KR20040108590A - Hard Coat Film, Production Method of The Same, Polarizing Plate and Display - Google Patents

Abstract

PURPOSE: Provided are a hard coating film, which has excellent hardness and shows uniform imaging resistance and excellent flatness even in the form of a thin film or broad film, and a method for manufacturing the same. CONSTITUTION: The hard coating film comprises a UV absorbing agent and at least two plasticizer and has an active ray-curable resin layer formed on a cellulose ester film. In the hard coating film, (i) one of the plasticizers is a polyhydric alcohol ester plasticizer and the other is a plasticizer other than phosphate ester plasticizers; (ii) the total acyl group substitution degree of the cellulose ester is 2.6-2.9; (iii) the number average molecular weight(Mn) of the cellulose ester is 80,000-200,000; (iv) the ratio of Mw(weight average molecular weight)/Mn(number average molecular weight) of the cellulose ester is 1.4-3.0; (v) the cellulose ester film is a biaxially oriented film; and (vi) the active-ray curable resin is applied on the film and then cured by irradiating it.

Description

Hard coat film, its manufacturing method, polarizing plate and display device {Hard Coat Film, Production Method of The Same, Polarizing Plate and Display}

This invention relates to the hard coat film which has an active-line hardening resin layer on a specific cellulose ester film, its manufacturing method, the antireflection film using the same, the polarizing plate using the same, and a display apparatus.

Background Art In recent years, high-performance optical films have been demanded in which anti-reflective functions, antistatic functions, and the like are provided with full colorization of notebook PCs, mobile phones, and the like, and high definition of displays. The surface of the display is required to have many chances to be touched by hand and not to be scratched, and a hard coating layer is formed. In recent years, in order to improve visibility, it is required to provide antireflection property and antifouling property to the surface. For example, an optical film having a functional layer such as a metal oxide is developed on the cellulose ester film directly or through another layer. It is becoming. In addition, in order to reduce the thickness of the display device, it is increasingly required that the film thickness of the film to be used is gradually thinner, and that the width of the hard coating film is also required to be large in size. Especially in the large screen, the hard coating film which is excellent in flatness is calculated | required, but the conventional hard coating film was not able to obtain especially the flatness in the wide width | variety and the thin film, and also the sufficient thing in the large area also about flaw resistance.

For example, although the example which formed the ultraviolet curable resin layer on the cellulose-ester film containing a ultraviolet absorber is illustrated by patent document 1, since pencil hardness is only about 2H, it was not sufficient hardness.

In order to impart durability to the cellulose ester film, an ultraviolet absorber is added.

Generally, a hard coat film is formed as a layer of a film thickness of about 3-10 micrometers directly on a plastic film as above, or through the lower layer of about 0.1-1 micrometer. However, in the conventional hard coating film, the hardness of the hard coating layer was insufficient, and thus the hard coating layer was also deformed in accordance with the deformation of the base plastic base film, and the hardness of the entire hard coating film was not sufficiently satisfied. In the hard coat film which apply | coated the ultraviolet curable resin layer to said thickness on the cellulose-ester film, about 2H is common in pencil hardness, and sufficient hardness more than 4H could not be obtained.

On the other hand, Patent Document 2 discloses a method of increasing the pencil hardness by thickening the film thickness of the hard coating layer. Clearly, thickening the film thickness of the hard coating layer is effective for improving pencil hardness. However, when the thickness of the hard coating layer is made thick, not only the flatness is easily lowered but also the thickness of the thin coating for use in the thin display device may be hindered. In particular, the thickness of the hard coating layer may be 20 to 200 µm. have.

In addition, Patent Document 3 describes an example in which a hard coating layer is formed on a cellulose triacetate film containing an ultraviolet absorber, but these are only about 2H in pencil hardness, and thus, the level is not sufficient.

When forming an ultraviolet curable resin layer on the cellulose-ester film base material containing a ultraviolet absorber, there existed a problem that a film itself also generate | occur | produces and the base material deform | transforms according to the ultraviolet-ray to irradiate. In particular, in the thin film, in order to have the required ultraviolet absorbency, the content of the ultraviolet absorber must be increased, and the influence was remarkable. Moreover, when the width | variety of the base film became wider, it became difficult to irradiate an ultraviolet-ray uniformly to the width direction, and there existed a problem that a base material deform | transformed. If the irradiation amount is reduced due to fear of deformation of the substrate, sufficient light quantity may not be secured at a place close to the end, and thus the required hardness cannot be obtained. If the irradiation time is reduced by reducing the light quantity, there is a problem that the productivity is significantly reduced.

[Patent Document 1] Japanese Patent Application Laid-Open No. 2001-183528

[Patent Document 2] Japanese Patent Application Laid-Open No. 2003-57402

[Patent Document 3] Japanese Patent Application Laid-Open No. 2001-91705

1 is a view showing an example of a plasma discharge processing apparatus used to form the metal oxide layer of the present invention.

2 shows an example of a plasma discharge treatment apparatus having a rotating electrode and a fixed electrode useful for forming the metal oxide thin film layer of the present invention.

<Explanation of symbols for the main parts of the drawings>

F: hard coated film

G: reactive gas

G ′: exhaust gas

10A, 10B, 110: Rotating Electrode

11A, 11B, 11C, 11D: U-turn roll

20, 21: guide roll

30: reactive gas supply unit

40, 140: gas exhaust port

50, 150: discharge part

51: rectification plate

80, 180: power

81, 82, 181, 182: voltage supply means

111: fixed electrode

120, 121: guide roll

122, 123: Nip Roll

124, 125: partition plate

130: air supply pipe

131: reaction gas generator

190: plasma discharge vessel

A first object of the present invention is to provide a hard coating film having excellent hardness and a uniform flaw resistance and excellent planarity even at a thin film or a wide range, and a method for producing the same with good productivity. It is to provide an antireflection film having a markedly reduced color unevenness using a light emitting device, a polarizing plate having excellent flatness using them, and a display device having excellent flatness of the surface.

The above object of the present invention is achieved according to the following.

1. In the hard coat film which formed the active-line hardening resin layer on the cellulose-ester film containing a ultraviolet absorber and 2 or more types of plasticizers, 1 or more types of the said plasticizers are polyhydric alcohol ester plasticizers, and the other 1 type is phosphoric acid It is selected from plasticizers other than the ester plasticizer, and the cellulose ester film has a total acyl group substitution degree of 2.6 to 2.9, a number average molecular weight (Mn) of 80,000 to 200,000, and a weight average molecular weight (Mw) / number average molecular weight (Mn) of It is manufactured by casting a cellulose ester solution of 1.4 to 3.0 and then biaxially stretched, wherein the active line cured resin layer is coated with an active line cured resin on the cellulose ester film and then irradiated with an active line to form the active line cured resin Hard coating film characterized in that the cured.

2. The hard coat film according to the above item 1, wherein the actinic radiation curable resin is cured with an irradiation dose of the actinic radiation being 5 to 100 mJ / cm 2.

3. The hard coating film according to the above 1 or 2, wherein the roughness of the active line irradiation part for curing the active line cured resin is 50 to 150 mW / cm 2.

4. The plasticizer according to any one of the above items 1 to 3, wherein the plasticizer other than the phosphate ester plasticizer is selected from a citric acid ester plasticizer, a glycolate plasticizer, a phthalic ester plasticizer and a fatty acid ester plasticizer. Hard coating film made with.

5. The film thickness of the said cellulose ester film is 10-70 micrometers, The film thickness (H) of an active-line cured resin layer, and the film thickness of a cellulose ester film as described in any one of said 1-4. The ratio (d / H) of d) is 4-10, The hard coat film characterized by the above-mentioned.

6. The hard coat film according to any one of items 1 to 5, wherein the width of the cellulose ester film is in a range of 1.4 m to 4 m.

7. The polarizing plate which has the cellulose-ester film which has a phase difference on the back surface on the surface of the anti-reflective film which provided the anti-reflective layer on the hard coat film as described in any one of said 1-6.

8. The liquid crystal display device which provided the hard coat film in any one of said claim | item 1 -6 on the surface.

9. It has a polarizing plate of said claim | item 7, The liquid crystal display device characterized by the above-mentioned.

10. Plasticizers other than a ultraviolet absorber, at least one polyhydric alcohol ester plasticizer, a phosphate ester plasticizer, and a total acyl group substitution degree of 2.6 to 2.9, a number average molecular weight (Mn) of 80,000 to 200,000, and a weight average molecular weight (Mw) / The cellulose ester solution containing the cellulose ester whose number average molecular weight (Mn) value is 1.4-3.0 is cast on a support body, it is dried until it becomes peelable, and the state contains a solvent after peeling from a support body. The active wire cured resin is applied onto the cellulose ester film obtained by biaxial stretching and drying, and the active wire is irradiated to cure the active wire cured resin at a light amount of 5 to 100 mJ / cm 2. Method of producing a coated film.

11. The method according to the above 10, wherein the stretching of the cellulose ester film is stretched in the longitudinal direction (conveying direction) in a state containing a solvent after peeling off from the support, and then stretched in the transverse direction by tenters. Method for producing a hard coat film, characterized in that.

12. The method for producing a hard coat film according to the above 10 or 11, wherein the active line cured resin is cured while applying tension.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The present invention is a hard coating film in which an active line cured resin layer is formed on a cellulose ester film containing an ultraviolet absorber and two or more kinds of plasticizers, and the total acyl group substitution degree is 2.6 to 2.9, and the number average molecular weight (Mn) It is this 80,000-200,000, It is characterized by having the cellulose ester whose value of weight average molecular weight (Mw) / number average molecular weight (Mn) is 1.4-3.0.

The value of Mw / Mn of the cellulose ester in this invention is 1.4-3.0. In addition, in this invention, although the cellulose ester film should just contain the cellulose ester whose Mw / Mn value is 1.4-3.0 as a material, the cellulose ester (preferably cellulose triacetate or cellulose acetate propio which is contained in the protective film for polarizing plates) Nate) It is more preferable that the value of Mw / Mn of the whole is a range of 1.4-3.0. It is difficult to make it less than 1.4 in the synthesis | combination process of a cellulose ester, and although cellulose ester equipped with molecular weight can be obtained by fractionation by gel filtration etc., it is not preferable because it requires a considerable cost. On the other hand, if it exceeds 3.0, the effect of maintaining planarity is lowered. More preferably, they are 1.7-2.2.

Moreover, it is necessary for the number average molecular weight (Mn) of a cellulose ester to be 80,000-200,000.

If the molecular weight of a cellulose ester is large and there is little distribution of molecular weight, it is guessed that the plasticizer and ultraviolet absorber added at the time of apply | coating a hard coat layer will become difficult to elute. It is assumed that this effect will be further remarkable by oriented biaxially to the cellulose ester molecules in the transverse direction. It is also necessary that the degree of substitution of the cellulose ester is in the range of 2.6 to 2.9, and that an unsubstituted hydroxyl group remains in the cellulose main chain at an appropriate ratio is considered to contribute to preventing elution of the plasticizer and the ultraviolet absorber by hydrogen bonding or the like. . It is thought that one or more types of plasticizers are polyhydric alcohol ester plasticizers, and it is thought that the elution of another plasticizer is also prevented, and it is more effective than the case where it uses alone. When phosphate ester type plasticizer is contained, it is not only easy to elute itself, but also another plasticizer is easy to elute, and it is thought that planarity deteriorates because a plasticizer is taken out from a cellulose ester. Although the plasticizer to be used is not specifically limited, It is necessary to contain 2 or more types of plasticizers. In that case, it is necessary to be substantially free of the phosphate ester plasticizer generally used conventionally. It is preferable that content in a film is less than 1 mass%, that it does not contain substantially, Preferably it is less than 0.1 mass%, and it is preferable that it is 0 mass% (below detection limit). That is, containing 2 or more types of said plasticizers means containing 2 or more types of plasticizers other than a phosphate ester type.

The hard coat layer of this invention is one of the characteristics that 4H or more is obtained by pencil hardness as hardness, and it is excellent in planarity. Surprisingly, even when the amount of ultraviolet irradiation at the time of curing the hard coat layer is low, hardness above conventional can be obtained. Since the hardness can be obtained even if the amount of ultraviolet irradiation is reduced, the heat generation of the ultraviolet absorber and the hard coating layer itself in the cellulose ester film caused by ultraviolet irradiation can be suppressed, and a hard coating film excellent in flatness can be obtained, and the productivity is dramatically improved. Confirmed. In particular, a hard coat film having a pencil hardness of 4H or higher can be obtained at an irradiation dose of 100 mJ / cm 2 or less.

Hereinafter, the present invention will be described in more detail.

<Cellulose ester>

The molecular weight of the cellulose ester used for this invention is a thing of 80,000-200,000 as a number average molecular weight (Mn). It is more preferable that it is 100,000-200,000, and 150,000-200,000 are especially preferable.

As for the cellulose ester used by this invention, ratio of weight average molecular weight (Mw) and number average molecular weight (Mn), Mw / Mn is 1.4-3.0 as mentioned above, Preferably it is 1.7-2.2.

The average molecular weight and molecular weight distribution of the cellulose ester can be measured by a known method using high performance liquid chromatography. A number average molecular weight and a weight average molecular weight can be calculated using this, and the ratio (Mw / Mn) can be calculated.

Measurement conditions are as follows.

Solvent: Methylene Chloride

Column: Shodex K806, K805, K803G (3 products from Showa Electric Co., Ltd. were used)

Column temperature: 25 ℃

Sample concentration: 0.1 mass%

Detector: RI Model 504 (GL Sciences Inc.)

Pump: L6000 (manufactured by Hitachi, Ltd.)

Flow rate: 1.0 ml / min

Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Samso Co., Ltd.) Mw = 1,000,000 to 500 calibration curves using 13 samples were used. 13 samples are preferably obtained at approximately equal intervals.

The cellulose ester used for this invention is a C2-C22 carboxylic acid ester, It is especially preferable that it is a lower fatty acid ester of cellulose.

Lower fatty acids in lower fatty acid esters of cellulose mean fatty acids having 6 or less carbon atoms, for example, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate phthalate, and the like. Mixed fatty acid esters, such as cellulose acetate propionate and cellulose acetate butyrate, as described in US Pat. No. 8-231761, US Pat. No. 2,319,052, and the like can be used. The lower fatty acid ester of cellulose used especially preferably among the said base materials is cellulose triacetate and cellulose acetate propionate. These cellulose esters can also be mixed and used.

In the case of cellulose triacetate, those having a total acyl group substitution degree (acetyl group substitution degree) of 2.6 to 2.9 are preferably used.

Preferred cellulose esters other than cellulose triacetate have acyl groups having 2 to 4 carbon atoms as substituents, when the degree of substitution of the acetyl group is X and the degree of substitution of the propionyl group is Y, the following formulas (I) and (II) ) Is a cellulose ester that satisfies at the same time.

Equation (I) 2.6≤X + Y≤2.9

Equation (II) 0≤X≤2.5

Especially, the cellulose acetate propionate (total acyl-group substitution degree = X + Y) whose 1.9 <= <= <= 2.5, 0.1 <= Y <= 0.9 is preferable. The part which is not substituted by the acyl group exists normally as a hydroxyl group. These can be synthesized by a known method.

These acyl group substitution degree can be measured according to the method of the prescription | regulation to ASTM-D 817-96.

The cellulose ester may be used alone or in combination with a cellulose ester synthesized from cotton linter, wood pulp, Kenaf, or the like as a raw material. In particular, cotton linter (hereinafter, sometimes referred to simply as linter) and cellulose ester synthesized from wood pulp are preferably used alone or in combination.

In addition, the cellulose ester obtained from these can be mixed and used in arbitrary ratios, respectively. These cellulose esters are prepared by using a cellulose raw material, using an organic solvent such as acetic acid or an organic solvent such as methylene chloride when the acylating agent is an acid anhydride (acetic anhydride, propionic anhydride, butyric anhydride), and using a protic catalyst such as sulfuric acid. It can be obtained by reacting accordingly.

In the case of acetyl cellulose, it is necessary to extend the time of the acetization reaction in order to increase the acetization rate. However, if the reaction time is too long, decomposition proceeds simultaneously, resulting in breakage of the polymer chain, decomposition of the acetyl group, and the like, which leads to undesirable results. Therefore, in order to increase the degree of acetization and to suppress decomposition to some extent, it is necessary to set the reaction time in a certain range. It is not appropriate to define the reaction time because the reaction conditions vary, and the reaction conditions, equipment and other conditions greatly change. As the decomposition of the polymer proceeds, the molecular weight distribution becomes wider, and therefore, even in the case of cellulose ester, the degree of decomposition can be defined by the value of the weight average molecular weight (Mw) / number average molecular weight (Mn) that is usually used. That is, in the process of acetonitrile of cellulose triacetate, it is too long so that decomposition does not progress excessively, and the weight average molecular weight used as an indicator of the degree of reaction for carrying out the acetization reaction for a sufficient time for acetization ( The value of Mw) / number average molecular weight (Mn) can be used.

When an example of the manufacturing method of a cellulose ester is shown below, 100 mass parts of cotton linters were disintegrated as a cellulose raw material, 40 mass parts of acetic acid were added, and pretreatment activation was performed at 36 degreeC for 20 minutes. Then, 8 mass parts of sulfuric acid, 260 mass parts of acetic anhydride, and 350 mass parts of acetic acid were added, and esterification was performed at 36 degreeC for 120 minutes. After neutralizing with 11 parts by mass of an aqueous 24% magnesium acetate solution, saponification was aged for 35 minutes at 63 ° C to obtain acetyl cellulose. The mixture was stirred at room temperature for 160 minutes using 10 times aqueous acetic acid solution (acetic acid: water = 1: 1 (mass ratio)), followed by filtration and drying to obtain purified acetyl cellulose having an acetyl substitution degree of 2.75. This acetyl cellulose had Mn of 92,000, Mw of 156,000 and Mw / Mn of 1.7. Similarly, cellulose esters with different degrees of substitution and Mw / Mn ratio can be synthesized by adjusting esterification conditions (temperature, time, stirring) and hydrolysis conditions of cellulose esters. In addition, the synthesized cellulose ester is preferably purified to remove low molecular weight components or to remove the microacetized components by filtration.

In addition, in the case of a mixed acid cellulose ester, it can react and obtain by the method of Unexamined-Japanese-Patent No. 10-45804. The measuring method of substitution degree of an acyl group can be measured according to the prescription | regulation of ASTM-D 817-96.

In addition, the cellulose ester is also affected by the trace metal component in the cellulose ester. Although these are considered to be related to water used in the manufacturing process, it is preferable that fewer components can be insoluble nuclei, and metal ions such as iron, calcium, and magnesium may contain organic acid groups. Insolubility may be formed by forming a salt etc., and few are preferable. About an iron (Fe) component, it is preferable that it is 1 ppm or less. About calcium (Ca) component, it is contained a lot in groundwater, river water, etc., and when this is large, it becomes hard water and it is inadequate as a drink, but it forms acidic components, such as carboxylic acid and sulfonic acid, and also many ligands and coordination compounds, ie complexes It is easy and forms a scum derived from many insoluble calcium.

Calcium (Ca) component is 60 ppm or less, Preferably it is 0-30 ppm. About too much magnesium (Mg) component, since insoluble content will generate | occur | produce, it is preferable that it is 0-70 ppm, and it is especially preferable that it is 0-20 ppm. Metal components such as iron (Fe) content, calcium (Ca) content, and magnesium (Mg) content include pre-treatment of the completely dried cellulose ester with a micro digest wet decomposition device (sulfuric acid decomposition) and alkali melting. It can obtain | require by carrying out analysis using ICP-AES (inductively coupled plasma emission spectroscopy apparatus).

<Plasticizer>

The cellulose ester film used by this invention contains 2 or more types of plasticizers. In addition, the cellulose ester film practically does not contain a phosphate ester plasticizer such as triphenyl phosphate. The term “substantially free” means that the content of the phosphate ester plasticizer is less than 1% by mass, preferably 0.1% by mass, and particularly preferred is not added.

Elution of a plasticizer can be reduced by containing 2 or more types of plasticizers. Although the reason is not clear, it is thought that elution is suppressed by the addition amount per type and interaction with two plasticizers and a cellulose ester.

The two plasticizers are not particularly limited, but are preferably selected from the above polyhydric alcohol ester plasticizers, phthalic acid esters, citric acid esters, fatty acid esters, glycolate plasticizers, and the like. Among them, at least one kind is preferably a polyhydric alcohol ester plasticizer.

The polyhydric alcohol ester plasticizer is a plasticizer composed of an ester of a divalent or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule, preferably a 2 to 20 valent aliphatic polyhydric alcohol ester. .

The polyhydric alcohol used for this invention is represented by following General formula (1).

R _1- (OH) _n

Provided that R ₁ is an n-valent organic group, n is a positive integer of 2 or more, and the OH group represents an alcoholic and / or phenolic hydroxyl group.

As an example of a preferable polyhydric alcohol, although the following is mentioned, for example, this invention is not limited to these. Adonitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, galactitol, mannitol, 3-methylpentane-1,3,5-triol, pinacol, sorbitol, trimethylol propane, trimethylol ethane, xylitol and the like. In particular, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylol propane and xylitol are preferable.

There is no restriction | limiting in particular as monocarboxylic acid used for the polyhydric alcohol ester of this invention, A well-known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid, etc. can be used. When alicyclic monocarboxylic acid and aromatic monocarboxylic acid are used, it is preferable at the point which improves moisture permeability and retention property.

Examples of the preferred monocarboxylic acid include the following, but the present invention is not limited thereto.

As the aliphatic monocarboxylic acid, a fatty acid having a straight or branched chain having 1 to 32 carbon atoms can be preferably used. As for carbon number, it is more preferable that it is 1-20, and it is especially preferable that it is 1-10. When acetic acid is contained, compatibility with a cellulose ester increases, and it is preferable, and it is also preferable to mix and use acetic acid and another monocarboxylic acid.

Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelagonic acid, capric acid, 2-ethylhexanoic acid, undecyl acid, lauric acid, tride Real acid, myristic acid, pentadecyl acid, palmitic acid, heptadecyl acid, stearic acid, nonadecanoic acid, arachnic acid, behenic acid, lignocerinic acid, sertoic acid, heptaconic acid, montanic acid, melisic acid And unsaturated fatty acids such as saturated fatty acids such as lacxel acid, undecylenic acid, oleic acid, sorbic acid, linoleic acid, linoleic acid, and arachidonic acid.

Examples of preferred alicyclic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, and derivatives thereof.

As an example of a preferable aromatic monocarboxylic acid, the thing which introduce | transduced the alkyl group in the benzene ring of benzoic acid, such as benzoic acid and toluic acid, and two or more benzene rings, such as biphenyl carboxylic acid, naphthalene carboxylic acid, and tetralin carboxylic acid, are introduced. The aromatic monocarboxylic acid which has, or derivatives thereof is mentioned. Especially benzoic acid is preferable.

Although the molecular weight of polyhydric alcohol ester does not have a restriction | limiting in particular, It is preferable that it is 300-1,500, and it is more preferable that it is 350-750. Since the larger molecular weight is less likely to volatilize, it is preferable, and the smaller one is preferable from the viewpoint of moisture permeability and compatibility with a cellulose ester.

The carboxylic acid used for a polyhydric alcohol ester may be one type, or 2 or more types may be mixed. In addition, all the OH groups in the polyhydric alcohol may be esterified, and some may be left as OH groups.

Below, the specific compound of polyhydric alcohol ester is illustrated.

Although the glycolate plasticizer is not specifically limited, Alkylphthalyl alkyl glycolates can be used preferably. Examples of the alkyl phthalyl alkyl glycolates include methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, and methyl phthalyl. Ethyl glycolate, ethylphthalylmethyl glycolate, ethylphthalylpropyl glycolate, methylphthalylbutyl glycolate, ethylphthalylbutyl glycolate, butylphthalylmethyl glycolate, butylphthalylethyl glycolate, propylphthalylbutyl Glycolate, butylphthalylpropyl glycolate, methylphthalyloctyl glycolate, ethylphthalyloctyl glycolate, octylphthalylmethyl glycolate, octylphthalylethyl glycolate, and the like.

Examples of the phthalic ester plasticizer include diethyl phthalate, dimethoxy ethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, dicyclohexyl terephthalate, and the like. Can be mentioned.

Examples of citric acid ester plasticizers include acetyl trimethyl citrate, acetyl triethyl citrate, and acetyl tributyl citrate.

Examples of the fatty acid ester plasticizers include butyl oleate, methylacetyl risinol, dibutyl sebacinate, and the like.

Examples of the phosphate ester plasticizer include triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, octyldiphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, and the like. It does not contain substantially in the cellulose-ester film which comprises this invention. As mentioned above, it is especially preferable that content is substantially less than 1 mass%, Preferably it is less than 0.1 mass%, and does not contain at all that it does not contain substantially.

As described above, when the phosphate ester plasticizer is included, the substrate is easily deformed when the hard coating layer is formed, which is not preferable.

As for the total content of the plasticizer in a cellulose ester film, 5-20 mass% is preferable with respect to solid content total amount, 6-16 mass% is more preferable, Especially preferably, it is 8-13 mass%. Moreover, content of 2 types of plasticizers is at least 1 mass% or more, respectively, Preferably it contains 2 mass% or more, respectively.

It is preferable to contain 1-12 mass% of polyhydric-alcohol ester plasticizers, and it is preferable to contain 3-11 mass% especially. If it is small, planar deterioration is seen, and if too much, it is easy to bleed out. It is preferable that it is the range of 1: 4-4: 1, and, as for the ratio of a polyhydric-alcohol ester plasticizer and another plasticizer, it is more preferable that it is 1: 3-3: 1. Even if there is too much addition amount of a plasticizer, at least a film is easy to deform | transform and it is not preferable.

<Ultraviolet absorber>

The cellulose ester film according to the present invention contains a ultraviolet absorber. The ultraviolet absorber aims at improving durability by absorbing ultraviolet rays of 400 nm or less. Particularly, the transmittance at a wavelength of 370 nm is preferably 10% or less, more preferably 5% or less, even more preferably 2%. It is as follows.

Although the ultraviolet absorber used for this invention is not specifically limited, For example, an oxybenzo phenone type compound, a benzo triazole type compound, a salicylic acid ester type compound, a benzophenone type compound, a cyanoacrylate type compound, a triazine type compound, a nickel complex salt A system compound, an inorganic powder, etc. are mentioned.

The ultraviolet absorber used preferably is a benzotriazole type ultraviolet absorber or a benzophenone type ultraviolet absorber which is highly transparent, and is excellent in the effect which prevents deterioration of a polarizing plate or a liquid crystal element, and the benzotriazole type ultraviolet absorber which has less unnecessary coloring is especially preferable. Do. As a specific example of the ultraviolet absorber used for this invention, 5-chloro-2- (3,5-di-sec- butyl- 2-hydroxyphenyl) -2H- benzotriazole, (2-2H- Benzotriazol-2-yl) -6- (linear and branched dodecyl) -4-methylphenol, 2-hydroxy-4-benzyloxybenzophenone, 2,4-benzyloxybenzophenone, and the like Tinuvin, such as Nuvin 109, Tinuvin 171, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, and the like, all of which can be preferably used as commercial products of Ciba Specialty Chemicals.

Moreover, the triazine type compound represented by General formula (I) of Unexamined-Japanese-Patent No. 2001-235621 is also used suitably for the cellulose ester film which concerns on this invention.

It is preferable that the cellulose ester film which concerns on this invention contains 2 or more types of ultraviolet absorbers.

As the ultraviolet absorber, a polymeric ultraviolet absorber can also be preferably used, and in particular, a polymer ultraviolet absorber of JP-A-6-148430 is preferably used.

The addition method of a ultraviolet absorber is added to dope after melt | dissolving a ultraviolet absorber in organic solvents, such as methanol, ethanol, butanol, methylene chloride, methyl acetate, acetone, and dioxolane, or a mixed solvent thereof, or dope directly It can also be added during composition. What does not dissolve in an organic solvent like an inorganic powder is added to dope after disperse | distributing in an organic solvent and a cellulose ester using a dissolving group or a sand mill.

Although the usage-amount of a ultraviolet absorber is not the same according to the kind of a ultraviolet absorber, a use condition, etc., when the dry film thickness of a cellulose ester film is 30-200 micrometers, 0.5-4.0 mass% is preferable with respect to a cellulose ester film, and 0.6- 2.0 mass% is more preferable.

<Particulates>

The cellulose ester film according to the present invention preferably contains fine particles.

As fine particles used in the present invention, examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and phosphoric acid Calcium is mentioned. It is preferable that microparticles | fine-particles contain silicon in the point that turbidity becomes low, and especially silicon dioxide is preferable.

5-50 nm is preferable and, as for the average diameter of the primary particle of microparticles | fine-particles, 7-20 nm is more preferable. It is preferable to contain these mainly as a secondary aggregate with a particle diameter of 0.05-0.3 micrometers. It is preferable that content of these microparticles | fine-particles in a cellulose ester film is 0.05-1 mass%, and 0.1-0.5 mass% is especially preferable. In the case of the cellulose-ester film of a multilayered structure by a co-combustion method, it is preferable to contain the said addition amount microparticles on the surface.

The fine particles of silicon dioxide are commercially available under the trade names of, for example, Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, and TT600 (manufactured by Nippon Aerosol Co., Ltd.).

The fine particles of zirconium oxide are commercially available under the trade names of, for example, Aerosol R976 and R811 (above, Aerosol Co., Ltd.).

Examples of the polymer include silicone resins, fluororesins and acrylic resins. A silicone resin is preferable and it is preferable to have a three-dimensional network structure especially, for example, Tospur 103, 105, 108, 120, 145, 3120, and 240 (above Toshiba Silicone Co., Ltd. product). It is marketed under a brand name of) and can use it.

Among them, aerosol 200V and aerosol R972V are particularly preferably used because the effect of lowering the friction coefficient is great while keeping the turbidity of the cellulose ester film low. In the cellulose ester film used by this invention, it is preferable that the dynamic friction coefficient of the back surface side of a hard-coat layer is 1.0 or less.

<Dye>

Dye may be added to the cellulose ester film used by this invention for color adjustment. For example, a blue dye may be added in order to suppress the yellowness of a film. Preferred dyes include anthraquinone dyes.

The anthraquinone dye may have any substituent at any position from 1 to 8 positions of the anthraquinone. Preferable substituents include an anilino group, a hydroxyl group, an amino group, a nitro group or a hydrogen atom. In particular, it is preferable to contain blue dye, especially anthraquinone type dye of Unexamined-Japanese-Patent No. 2001-154017.

Various additives may be added to dope which is a cellulose ester containing solution before film forming, and an additive dissolution liquid may be prepared separately and added in line. Particularly, in order to reduce the load on the filter medium, it is preferable to add a part or the whole amount inline.

When adding an additive solution inline, in order to improve the mixing property with dope, it is preferable to melt | dissolve a small amount of cellulose esters. The amount of preferable cellulose ester is 1-10 mass parts with respect to 100 mass parts of solvents, More preferably, it is 3-5 mass parts.

In order to perform in-line addition and mixing in this invention, in-line mixers, such as a static mixer (Tore engineering product) and SWJ (Tore static tube mixer Hi-Mixer), etc. are used preferably.

<Method for producing cellulose ester film>

Next, the manufacturing method of the cellulose ester film of this invention is demonstrated.

The manufacture of the cellulose ester film of this invention is a process of manufacturing a dope by dissolving a cellulose ester and an additive in a solvent, the process of cast | flow_spreading on the endless metal support body which transfers dope infinitely, and a flexible dope. It is carried out according to the process of drying as a web, the process of peeling from a metal support body, the process of extending | stretching or holding width, the process of further drying, and the process of winding up a completed film.

The process of manufacturing dope is demonstrated. The concentration of the cellulose ester in the dope is preferably thick, and the drying load can be reduced after being flexible to the metal support. However, if the concentration of the cellulose ester is too high, the load during filtration increases and the filtration accuracy becomes worse. As a density | concentration which makes these compatible, 10-35 mass% is preferable, More preferably, it is 15-25 mass%.

Although the solvent used by the dope of this invention may be used individually or in combination, It is preferable to mix and use the good solvent and poor solvent of a cellulose ester from a viewpoint of a production efficiency, and the one with many good solvents has the viewpoint of the solubility of a cellulose ester. Preferred at The preferable ranges of the mixing ratio of a good solvent and a poor solvent are 70-98 mass% of good solvents, and 2-30 mass% of poor solvents. A good solvent and a poor solvent are defined as a poor solvent which melt | dissolves the cellulose ester to be used independently and swells alone or does not melt | dissolve alone. Therefore, a good solvent and a poor solvent change according to the average degree of aceticization (acetyl group substitution degree) of a cellulose ester, For example, when using acetone as a solvent, the acetic acid ester of a cellulose ester (acetyl group substitution degree 2.4), cellulose acetate In propionate, it becomes a good solvent, and in acetic acid ester of cellulose (acetyl group substitution degree 2.8), it becomes a poor solvent.

Although the good solvent used for this invention is not specifically limited, Organic halogen compounds, such as methylene chloride, dioxolane, acetone, methyl acetate, acetoacetic acid methyl, etc. are mentioned. Especially preferably, methylene chloride or methyl acetate is mentioned.

In addition, the poor solvent used for this invention is not specifically limited, For example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone, etc. are used preferably. Moreover, it is preferable that 0.01-2 mass% of water is contained in dope.

As a dissolution method of the cellulose ester at the time of preparing the dope of the said base material, the general method can be used. Combining heating and pressurization enables heating above the boiling point at normal pressure. It is preferable to melt and dissolve above the boiling point at the normal pressure of the solvent while heating to a temperature in which the solvent does not boil under pressure, since it prevents the formation of gels or bulky debris called lumps. In addition, a method in which the cellulose ester is mixed with the poor solvent to wet or swell, followed by further adding a good solvent to dissolve it is also preferably used.

Pressurization can also be performed by the method of press-fitting inert gas, such as nitrogen gas, or the method of raising the vapor pressure of a solvent by heating. Heating is preferably performed externally. For example, a jacket type is preferable because of easy temperature control.

The higher the heating temperature after the addition of the solvent is preferable from the viewpoint of the solubility of the cellulose ester, but if the heating temperature is too high, the required pressure becomes large, resulting in poor productivity. Preferable heating temperature is 45-120 degreeC, 60-110 degreeC is more preferable, and 70 degreeC-105 degreeC is still more preferable. In addition, the pressure is adjusted so that the solvent does not boil at the set temperature.

Alternatively, a cooling dissolution method is also preferably used, whereby the cellulose ester can be dissolved in a solvent such as methyl acetate.

Next, this cellulose ester solution is filtered using a suitable filter medium such as filter paper. As a filter medium, although absolute filtration precision is preferable in order to remove an insoluble matter etc., there exists a problem that blocking of a filter medium is easy to occur when absolute filtration precision is too small. For this reason, the filter medium of 0.008 mm or less of absolute filtration precision is preferable, A 0.001-0.008 mm filter medium is more preferable, A 0.003-0.006 mm filter medium is still more preferable.

There is no restriction | limiting in particular in the material of a filter medium, Although a normal filter medium can be used, The filter medium made from plastics, such as a polypropylene and Teflon (R), and the metal filter material, such as stainless steel, are preferable because there is no fallout of a fiber. It is preferable to remove and reduce the impurities contained in the cellulose ester of the raw material, in particular, the bright point foreign matter, by filtration.

With a bright point foreign material, two polarizing plates are arrange | positioned in cross nicol state, the cellulose-ester film is put in between, the light is irradiated from one polarizing plate side, and the light from the opposite side is counted when observed from the other polarizing plate side. It is a point (foreign material), and it is preferable that the number of bright spots whose diameter is 0.01 mm or more is 200 pieces / cm <2> or less. More preferably, it is 100 pieces / cm <2> or less, More preferably, it is 50 pieces / m <2> or less, More preferably, it is 0-10 pieces / cm <2> or less. Moreover, it is more preferable that the bright point of 0.01 mm or less is also small.

The dope can be filtered by a conventional method, but the method of filtration while heating at a temperature not lower than the boiling point at the normal pressure of the solvent and at a temperature in which the solvent does not boil under pressure is referred to as a differential pressure before and after filtration (called a differential pressure). The rise of is small and preferable. Preferable temperature is 45-120 degreeC, 45-70 degreeC is more preferable, It is more preferable that it is 45-55 degreeC.

It is preferable that the pressurization pressure is smaller. The pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and even more preferably 1.0 MPa or less.

Here, the softness of the dope will be described.

It is preferable that the surface of the metal support body in the casting process is mirror-finished, and as a metal support, the drum which plated the surface with the stainless steel belt or the casting is used preferably. The width of the cast can be 1 to 4 m. The surface temperature of the metal support in the casting step is -50 ° C. to a temperature below the boiling point of the solvent. A higher temperature is preferable to speed up the drying speed of the web. However, if the temperature is too high, the web foams or the planarity deteriorates. There is. Preferable support body temperature is 0-40 degreeC, and 5-30 degreeC is more preferable. Or it is also a preferable method to gelatinize a web and to peel from a drum in the state containing many residual solvents by cooling. The method of controlling the temperature of the metal support is not particularly limited, but there is a method of spraying hot or cold air or a method of bringing hot water into contact with the back side of the metal support. Since the use of warm water makes heat transfer more efficient, the time until the temperature of the metal support becomes constant is preferable. When using warm air, the wind of temperature higher than the target temperature may be used.

In order for a cellulose-ester film to show favorable planarity, the amount of residual solvent at the time of peeling a web from a metal support body is 10-150 mass%, More preferably, it is 20-40 mass% or 60-130 mass%, Especially preferably, it is 20-30 mass% or 70-120 mass%.

In the present invention, the residual solvent amount is defined by the following formula.

Residual Solvent Amount (Mass%) = M (M-N) / N｝ × 100

Here, M is the mass of the sample taken at the arbitrary time after manufacture of a web or a film, and N is the mass after heating M at 115 degreeC for 1 hour.

Moreover, in the drying process of a cellulose ester film, it is preferable to peel a web from a metal support body, and to further dry and to make residual solvent amount 1 mass% or less, More preferably, it is 0.1 mass% or less, Especially preferably, Is 0-0.01 mass% or less.

In the film drying process, generally, the method of drying, conveying a web by a roll drying method (the method of passing a web through several rolls arranged up and down alternately and drying) or a tenter system, can be employ | adopted.

In order to manufacture the cellulose ester film for hard-coating films of this invention, it extends to a conveyance direction in the place where the amount of residual solvents of a web immediately after peeling from a metal support is large, and also by the tenter system which grips both ends of a web with a clip etc. It is especially preferable to extend | stretch in the width direction. In the longitudinal direction and the transverse direction, the stretching ratio is preferably 1.05 to 1.3 times, more preferably 1.05 to 1.15 times. The area is preferably 1.12 times to 1.44 times and preferably 1.15 to 1.32 times by longitudinal and lateral stretching. This can be calculated | required by the draw ratio of a drawing direction of a longitudinal direction x a cross direction. When either of the stretching ratio in the longitudinal direction and the transverse direction is less than 1.05 times, the deterioration of planarity due to ultraviolet irradiation when forming the hard coating layer is large, which is not preferable. Moreover, even if a draw ratio exceeds 1.3 times, since planarity deteriorates and haze also increases, it is unpreferable.

In order to stretch in a longitudinal direction immediately after peeling, it is preferable to peel peeling tension at 210 N / m or more, Especially preferably, it is 220-300 N / m.

The means for drying the web is not particularly limited and generally can be performed by hot air, infrared rays, heating rolls, microwaves, etc., but is preferably performed by hot air from the viewpoint of simplicity.

It is preferable to make drying temperature in the drying process of a web step by step high at 40-150 degreeC, and performing in the range of 50-140 degreeC improves dimensional stability, and is more preferable.

Although the film thickness of a cellulose ester film is not specifically limited, 10-200 micrometers is used preferably. In particular, in the thin film having a thickness of 10 to 70 µm, it was difficult to obtain a hard coating film having excellent flatness and hardness, but according to the present invention, a hard coating film of a thin film having excellent flatness and hardness can be obtained, and the productivity is also excellent. It is especially preferable that the film thickness of a film is 10-70 micrometers. More preferably, it is 20-60 micrometers. Most preferably, it is 35-60 micrometers.

As for the hard coat film of this invention, the thing of width 1-4m is used preferably. When the width of the cellulose ester film becomes wider, the unevenness of irradiance of irradiated light at the time of ultraviolet curing cannot be ignored, and the flatness is not only deteriorated, but also the hardness unevenness occurs, and the reflection unevenness becomes remarkable when the antireflection layer is formed thereon. Had a problem. Since the hard coating film of this invention can obtain sufficient hardness with a small irradiation amount, even if there exists a nonuniformity of irradiation amount in the width direction of irradiation light, there is little hardness nonuniformity of the width direction, and since it is possible to obtain the hard coating film excellent also in planarity, it is a wide cellulose ester Remarkable effects are recognized in the film. Especially, the thing of width 1.4-4m is used preferably, Especially preferably, it is 1.4-2m. When it exceeds 4 m, conveyance will become difficult.

<Property>

The water vapor transmission rate of the cellulose ester film used in the present invention is 850 g / m 2 · 24h or less at 40 ° C. and 90% RH, preferably 20 to 800 g / m 2 · 24h, and particularly preferably 20 to 750 g / m 2 · 24h. . The water vapor transmission rate can be measured according to the method described in JIS Z 0208.

It is preferable that the elongation at break of the cellulose ester film used for this invention is 10 to 80%, and it is more preferable that it is 20 to 50%.

It is preferable that it is 90% or more, and, as for the visible light transmittance of the cellulose ester film used for this invention, it is more preferable that it is 93% or more.

It is preferable that it is less than 1%, and, as for the haze of the cellulose ester film used for this invention, it is especially preferable that it is 0 to 0.1%.

It is preferable that the in-plane retardation value Ro of the cellulose ester film used for this invention is 0-70 nm or less. More preferably, it is 0-30 nm or less, More preferably, it is 0-10 nm or less. It is preferable that the retardation value Rt of a film thickness direction is 400 nm or less, It is preferable that it is 10-200 nm, It is more preferable that it is 30-150 nm.

Retardation value Ro (Rt) can be calculated | required by the following formula | equation.

Ro = (nx-ny) × d

Rt = ((nx + ny) / 2-nz) × d

Here, d is the thickness (nm) of the film, the refractive index nx (the maximum refractive index in the plane of the film, also referred to as the refractive index in the slow axis direction), ny (in the direction perpendicular to the slow axis in the film plane) Refractive index) and nz (refractive index of the film in the thickness direction).

In addition, the retardation values Ro and Rt can be measured using an automatic birefringence meter. For example, it can obtain | require with wavelength 590nm in 23 degreeC and 55% RH environment using KOBRA-21ADH (Prince Measuring Machine Co., Ltd.).

Moreover, it is preferable that the slow axis exists in the width direction +/- 1 degree or the longitudinal direction +/- 1 degree of a film.

<Activation line cured resin layer>

The manufacturing method of the actinic-rays cured resin layer of the hard coat film of this invention is demonstrated.

In the hard coat film of this invention, an actinic-rays cured resin layer is used suitably as a hard coat layer.

An active ray hardening resin layer means the layer which has resin which hardens | cures through crosslinking reaction etc. by active ray irradiation, such as an ultraviolet-ray or an electron beam, as a main component. As active ray hardening resin, the component containing the monomer which has an ethylenically unsaturated double bond is used preferably, and it hardens | cures by irradiating an active ray, such as an ultraviolet-ray or an electron beam, and a hard-coat layer is formed. As active ray hardening resin, although ultraviolet curable resin, electron beam curable resin, etc. are mentioned as a typical thing, resin hardened | cured by ultraviolet irradiation is preferable.

As the ultraviolet curable resin, for example, an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin or an ultraviolet curable epoxy resin is preferably used. do.

UV-curable acrylurethane resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as methacrylate) in a product obtained by reacting an isocyanate monomer or a prepolymer with a polyester polyol. It can be obtained easily by further reacting an acrylate-based monomer having a hydroxyl group such as acrylate) and 2-hydroxypropyl acrylate. For example, the thing of Unexamined-Japanese-Patent No. 59-151110 can be used.

For example, a mixture of 100 parts of Unidick 17-806 (manufactured by Nippon Ink Co., Ltd.) and one part of Collonate L (manufactured by Nippon Polyurethane Co., Ltd.) and the like are preferably used.

As ultraviolet curing polyester acrylate type resin, what is generally formed is easily formed by making 2-hydroxyethyl acrylate and 2-hydroxy acrylate-type monomer react with polyester polyol, Unexamined-Japanese-Patent No. 59 The thing of -151112 can be used.

Specific examples of the ultraviolet curable epoxy acrylate resin include epoxy acrylate as an oligomer, and a reactive diluent and a photoreaction initiator are added to produce the reaction, and those described in Japanese Patent Application Laid-open No. Hei 1-105738 can be used. Can be.

Specific examples of the ultraviolet curable polyol acrylate resins include trimethylol propane triacrylate, ditrimethylol propane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and alkyl modified dipentaerythritol. Pentaacrylate and the like.

As a photoinitiator of these ultraviolet curable resins, benzoyl and its derivative (s), acetophenone, benzophenone, hydroxy benzophenone, Michler's ketone, (alpha)-amiroxime ester, thioxanthone, etc. are mentioned specifically, have. Can also be used with photosensitizers. The said photoreaction initiator can also be used as a photosensitizer. In addition, when using an epoxy acrylate type photoinitiator, sensitizers, such as n-butyl amine, triethyl amine, and tri-n-butyl phosphine, can be used. The photoreaction initiator or the photosensitizer used for the ultraviolet curable resin composition is 0.1-15 mass parts with respect to 100 mass parts of the composition, Preferably it is 1-10 mass parts.

As a resin monomer, general monomers, such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, styrene, are mentioned as a monomer which has one unsaturated double bond, for example. Moreover, as a monomer which has two or more unsaturated double bonds, Ethylene glycol diacrylate, propylene glycol diacrylate, divinyl benzene, 1, 4- cyclohexane diacrylate, 1, 4- cyclohexyl dimethyl diacrylate, the said Trimethylol propane triacrylate, pentaerythritol tetraacrylic ester, and the like.

As a commercial item of the ultraviolet curable resin which can be used in this invention, Adeka Optomer-KR-BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (Asa Hidenka Product); Koei hard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101, FT -102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Koei Chemical Co., Ltd.); Seika beam PHC2210 (S), PHC X-9 (K-3), PHC2213, DP-10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 Product); KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (made by Daicel UBCB Co., Ltd.); RC-5015, RC-5016, RC-5020, RC-5031, RC5100, RC-5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 Industrial Co., Ltd. product); Olex No. 340 Kuriya (manufactured by China Paint Co., Ltd.); Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (manufactured by Sanyo Chemical); SP-1509 and SP-1507 (manufactured by Showa Polymer Co., Ltd.); RCC-15C (Grace Japan Co., Ltd. product), Aronix M-6100, M-8030, M-8060 (Dong-A Synthetic Co., Ltd. product) etc. can be selected suitably, and can be used.

Specific examples of the compound include trimethylol propane triacrylate, ditrimethylol propane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl modified dipentaerythritol pentaacrylate, and the like. Can be mentioned.

These active-line cured resin layers can be apply | coated by well-known methods, such as a gravure coater, a dip coater, a reverse coater, a wire coater, a die coater, and the inkjet method.

As a light source for hardening an ultraviolet curable resin by a photocuring reaction, and forming a cured coating layer, it can use without limitation, if it is a light source which generate | occur | produces an ultraviolet-ray. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. Although irradiation conditions differ with each lamp | ramp, the irradiation amount of an active line becomes like this. Preferably it is 5-100mJ / cm <2>, Especially preferably, it is 20-80mJ / cm <2>.

In such a hard coating film, a hard coating film excellent in planarity with a pencil hardness of 4H or more was not obtained at such a low dose. In the case of a hard coating film whose hardness is not required very much, the dose can be further reduced, so that the hard coating film can be produced at a speed far exceeding the application speed limited by the ability of the ultraviolet irradiation unit, thereby significantly improving productivity. do.

Moreover, when irradiating an active line, it is preferable to carry out, providing a tension in the conveyance direction of a film, More preferably, it is performed, giving a tension also in the width direction. As for the tension | tensile_strength to provide, 30-300 N / m is preferable. The method of providing a tension is not specifically limited, A tension may be provided in a conveyance direction on a back roll, and a tension may be provided in a width direction or a biaxial direction by a tenter. Thereby, the film excellent in planarity can be obtained.

As an organic solvent of an ultraviolet curable resin layer composition coating liquid, hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), ketones (acetone, methyl ethyl ketone, methyl isobutyl, for example) Ketone), esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, and other organic solvents may be appropriately selected, or these may be mixed and used. 5 mass% or more, More preferably, 5-80 mass of propylene glycol monoalkyl ether (1-4 as carbon atom number of an alkyl group) or propylene glycol monoalkyl ether acetic acid ester (1-4 as carbon atom number of an alkyl group) etc. It is preferable to use the said organic solvent containing% or more.

Moreover, it is preferable to add a silicone compound especially to an ultraviolet curable resin layer composition coating liquid. For example, polyether modified silicone oil etc. are added preferably. As for the number average molecular weight of a polyether modified silicone oil, 1,000-100,000, Preferably 2,000-50,000 are suitable, When the number average molecular weight is less than 1,000, the dryness of a coating film falls, On the contrary, the number average molecular weight is 100,000 When it exceeds, it will become difficult to bleed out on the coating film surface.

Commercially available products of silicone compounds include DKQ8-779 (trade name of Dow Corning Corporation), SF3771, SF8410, SF8411, SF8419, SF8421, SF8428, SH200, SH510, SH1107, SH3749, SH3771, BX16-034, SH3746, SH3749, SH8400, SH3771M, SH3772M, SH3773M, SH3775M, BY-16-837, BY-16-839, BY-16-869, BY-16-870, BY-16-004, BY-16-891, BY-16-872 BY-16 -874, BY22-008M, BY22-012M, FS-1265 (above, product name of Torre Dow Corning Silicone Corporation), KF-101, KF-100T, KF351, KF352, KF353, KF354, KF355, KF615, KF618, KF945 , KF6004, Silicone X-22-945, X22-160AS (above, Shin-Etsu Chemical Co., Ltd. brand name), XF3940, XF3949 (above, Toshiba Silicone Co., Ltd. brand name), Disparon LS-009 (product of Kusumoto Chemical Co., Ltd.), Granol 410 (manufactured by Kyoisei Oil and Chemical Industry Co., Ltd.), TSF4440, TSF4441, TSF4445, TSF4446, TSF4452, TSF4460 (GE Toshiba Silicon Products), BYK-306, BYK-330, BYK-307, BYK-341, BYK-344, BYK-361 (manufactured by Big Chemi Japan Co., Ltd.), L series (e.g. L7001, L- 7006, L-7604, L-9000), Y series, FZ series (FZ-2203, FZ-2206, FZ-2207), etc. are mentioned, It is used preferably.

These components raise the applicability | paintability to a base material and an underlayer. When added to the laminate outermost surface layer, not only the water repellency, oil repellency, and antifouling property of the coating film are improved, but also the effect of damage to the frictional resistance of the surface is exerted. It is preferable to add these components in 0.01-3 mass% with respect to the solid content component in a coating liquid.

The above-mentioned thing can be used as a coating method of an ultraviolet curable resin composition coating liquid. 0.1-30 micrometers is suitable as a wet film thickness, Preferably it is 0.5-15 micrometers. Moreover, as dry film thickness, it is 0.1-10 micrometers, Preferably it is 1-10 micrometers.

More preferably, when the film thickness of a cellulose ester film is 10-70 micrometers and the ratio (d / H) of the film thickness (H) of a layer and the film thickness (d) of a cellulose ester film is 4-10, planarity is carried out. At the same time, it is excellent in hardness and scratch resistance. This is because when the hard coating layer is thinner than the film thickness of the cellulose ester, the hardness and flaw resistance are inferior, and when the hard coating layer is thicker than the film thickness of the cellulose ester, the planarity deteriorates.

The ultraviolet curable resin composition is preferably irradiated with ultraviolet rays during or after application drying, and as the irradiation time for obtaining the irradiation amount of the above-mentioned active line of 5 to 100 mJ / cm 2, about 0.1 second to about 5 minutes is preferable, and the curing efficiency of the ultraviolet curable resin or 0.1-10 second is more preferable from a viewpoint of work efficiency.

Moreover, it is preferable that the roughness of these active line irradiation parts is 50-150 mW / m <2>.

To the cured resin layer thus obtained, fine particles of an inorganic compound or an organic compound are used to prevent blocking, to increase frictional resistance, or the like, or to provide anti-glare properties and to adjust the refractive index. You can also add.

As inorganic fine particles used for the hard coat layer, silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate Can be mentioned. In particular, silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide and the like are preferably used.

As the organic fine particles, polymethacrylate methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicone resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, Melamine type resin powder, polyolefin type resin powder, polyester type resin powder, polyamide type resin powder, polyimide type resin powder, or poly ethylene fluoride type resin powder can be added to an ultraviolet curable resin composition. Particularly preferably, crosslinked polystyrene particles (e.g., SX-130H, SX-200H, SX-350H, manufactured by Shukku Chemical Co., Ltd.), polymethyl methacrylate particles (e.g., MX150, manufactured by Shukku Chemical Co., Ltd.), MX300).

As average particle diameter of these microparticles | fine-particles powder, 0.005-5 micrometers is preferable and it is especially preferable that it is 0.01-1 micrometer. It is preferable to mix | blend the ratio of an ultraviolet curable resin composition and fine particle powder so that it may be 0.1-30 mass parts with respect to 100 mass parts of resin compositions.

It is preferable that an ultraviolet curable resin layer is a clear hard coating layer whose center line average roughness (Ra) prescribed | regulated to JISB0601 is 1-50 nm, or Ra is an anti-glare layer about 0.1-1 micrometer. The center line average roughness Ra is preferably measured by an optical coherence surface roughness measuring instrument, and can be measured using, for example, RST / PLUS manufactured by WYKO Corporation.

<Back coating layer>

It is preferable to form a back coat layer on the surface on the opposite side to the side on which the hard coat layer of the hard coat film of the present invention is formed. The back coat layer is formed to correct curls formed by forming a hard coat layer or other layers by coating, CVD, or the like. That is, the degree of curl can be balanced by giving the property to round the surface on which the back coat layer is formed. In addition, the back coating layer is preferably applied as a blocking prevention layer, and in this case, it is preferable that fine particles are added to the back coating layer coating composition to impart a blocking prevention function.

Examples of the fine particles added to the back coating layer include inorganic compounds such as silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, tin oxide, indium oxide, zinc oxide, ITO, Hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. It is preferable that microparticles | fine-particles contain silicon from the point that haze becomes low, and silicon dioxide is especially preferable.

These microparticles | fine-particles are marketed and can be used, for example by brand name of aerosol R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (above Japan Aerosol Co., Ltd. product). The fine particles of zirconium oxide are commercially available under the trade names of, for example, Aerosol R976 and R811 (above, Aerosol Co., Ltd.). Examples of the polymer include silicone resins, fluororesins and acrylic resins. A silicone resin is preferable and it is preferable to have a three-dimensional network structure especially, for example, Tospur 103, 105, 108, 120, 145, 3120, and 240 (above Toshiba Silicone Co., Ltd. product). It is marketed under a brand name of) and can use it.

Among them, aerosol 200V and aerosol R972V are particularly preferably used because they have a large blocking prevention effect while keeping the haze low. As for the hard coat film used by this invention, it is preferable that the dynamic friction coefficient on the back surface side of a hard coat layer is 0.9 or less, especially 0.1-0.9.

Microparticles | fine-particles contained in a back coat layer are 0.1-50 mass% with respect to a binder, Preferably it is preferable that it is 0.1-10 mass%. It is preferable that the increase of haze at the time of forming a back coat layer is 1% or less, It is preferable that it is 0.5% or less, It is especially preferable that it is 0.0 to 0.1%.

The back coat layer is specifically made by apply | coating the composition containing the solvent which melt | dissolves a cellulose ester film, or the solvent which swells. The solvent to be used may further include a solvent which does not dissolve other than a mixture of a solvent to be dissolved and / or a solvent to be swelled, and a composition and an application amount of these mixed at an appropriate ratio depending on the degree of curl of the transparent resin film and the type of resin. To perform.

In order to enhance the curl prevention function, it is effective to increase the mixing ratio of the solvent for dissolving the solvent composition to be used and / or the solvent for swelling, and to reduce the ratio of the solvent that does not dissolve. This mixing ratio is preferably used (solvent to dissolve and / or solvent to swell): (solvent not to dissolve) = 10: 0 to 1: 9. As a solvent which melt | dissolves or swells the transparent resin film contained in such a mixed composition, For example, dioxane, acetone, methyl ethyl ketone, N, N- dimethylformamide, methyl acetate, ethyl acetate, trichloroethylene, methylene Chloride. Ethylene chloride, tetrachloroethane, trichloroethane, chloroform and the like. Examples of the solvent that does not dissolve include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butanol or hydrocarbons (toluene, xylene, cyclohexane).

It is preferable to apply these coating compositions with a wet film thickness of 1 to 100 µm on the surface of the transparent resin film using a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, and the like. desirable. Examples of the resin used as the binder for the back coating layer include, for example, vinyl chloride-vinyl acetate copolymer, vinyl chloride resin, vinyl acetate resin, copolymers of vinyl acetate and vinyl alcohol, partially hydrolyzed vinyl chloride-vinyl acetate copolymers, Vinyl polymers such as vinyl chloride-vinylidene chloride copolymer, vinylacrylonitrile chloride copolymer, ethylene-vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, or air Cellulose derivatives such as coalescing, nitrocellulose, cellulose acetate propionate (preferably acetyl group substitution degree 1.8 to 2.3, propionyl group substitution degree 0.1 to 1.0), diacetyl cellulose, cellulose acetate butyrate resin, maleic acid and / or acrylic acid Copolymer, acrylic ester copolymer, arc Ronitrile-styrene copolymer, chlorinated polyethylene, acrylonitrile-chlorinated polyethylene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylic resin, polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane Resins such as resins, polyether polyurethane resins, polycarbonate polyurethane resins, polyester resins, polyether resins, polyamide resins, amino resins, styrene-butadiene resins, butadiene-acrylonitrile resins, silicone resins, fluorine resins Although these etc. are mentioned, It is not limited to these. For example, as acrylic resin, Acripet MD, VH, MF, V (made by Mitsubishi Rayon Co., Ltd.), Hipearl M-4003, M-4005, M-4006, M-4202, M-5000, M -5001, M-4501 (product of Negami Kogyo Co., Ltd.), diamond BR-50, BR-52, BR-53, BR-60, BR-64, BR-73, BR-75, BR-77, BR- 79, BR-80, BR-82, BR-83, BR-85, BR-87, BR-88, BR-90, BR-93, BR-95, BR-100, BR-101, BR-102, Acrylic of BR-105, BR-106, BR-107, BR-108, BR-112, BR-113, BR-115, BR-116, BR-117, BR-118, etc. (manufactured by Mitsubishi Rayon Co., Ltd.) And various homopolymers and copolymers produced using methacrylic monomers as raw materials are commercially available, and preferred ones can be appropriately selected from these.

Especially preferably, it is a cellulose resin layer, such as diacetyl cellulose and cellulose acetate propionate.

The order of applying the back coating layer is irrelevant before or after applying the layer on the opposite side to the back coating layer of the cellulose ester film (a layer such as a clear hard coating layer or other antistatic layer), but the back coating layer also serves as a blocking prevention layer. In this case, it is preferable to apply first. Alternatively, the back coating layer may be applied in two or more times.

The hard coat film of this invention is suitable for uniformly forming the thin film of a metal compound layer by application | coating or plasma CVD method, especially atmospheric pressure plasma processing method, and these are useful as an antireflection layer.

As the atmospheric pressure plasma treatment method, for example, an atmospheric pressure plasma discharge treatment method for applying a high frequency pulse voltage described in JP-A-11-181573, JP-A-2000-26632, 2002-110397 and the like can be used. Further, the conductive layer can be formed by the atmospheric pressure plasma discharge treatment method described in Japanese Patent Laid-Open No. 2001-337201. Alternatively, the antireflection layer can be formed by the methods described in Japanese Patent Application Laid-Open No. 2002-228803, Japanese Patent Application 2002-369679, Japanese Patent Application 2002-317883, and Japanese Patent Application 2003-50823. Alternatively, an antifouling layer can be formed by the method described in Japanese Patent Application No. 2003-50823. Alternatively, the antireflection layer can be applied by the methods described in Japanese Patent Application Laid-Open No. 2003-93963 and Japanese Patent Application No. 2002-49724.

Metal compound in the atmosphere of the coating formed on the hard film of the present invention, in particular, most of the nitrogen gas (for example, _{SiO x, SiO x N y,} TiO x N y, SiO x C z (x = 1~2, y = 0.1~ Among the metal oxides, metal nitrides, metal oxynitrides, and metal carbides such as 1, z = 0.1 to 2), it is preferable to form a thin film of metal oxide or the like. Nitrogen gas contained in gas is 60 to 99.9 volume%, Preferably it is 75 to 99.9 volume%, More preferably, it is 90 to 99.9 volume%. In addition to nitrogen gas, an inert gas such as argon or helium may be contained, a gas of a metal compound for forming a thin film is contained, and a gas for promoting a reaction such as oxygen or hydrogen (also called an additive gas or an auxiliary gas). Etc. are contained. These can form a low refractive index layer, a high refractive index layer, a medium refractive index layer, a transparent conductive layer, an antistatic layer, an antifouling layer, etc. containing a metal compound.

Next, the antireflection layer formed on these hard coat layers will be described.

(Reflective layer)

In the present invention, the method for forming the antireflection layer is not particularly limited, and can be formed by coating, sputtering, vapor deposition, or CVD (chemical vapor deposition).

As a method of forming an anti-reflection layer by coating, a method of dispersing and drying a powder of a metal oxide in a binder resin dissolved in a solvent, a method of using a polymer having a crosslinked structure as a binder resin, containing an ethylenically unsaturated monomer and a photopolymerization initiator And the method of forming a layer by irradiating an actinic light, etc. are mentioned.

In this invention, a metal oxide layer can be formed on the hard coat film which provided the hard coat layer. A low refractive index metal oxide layer is formed on the top layer of the hard coating film, and a high refractive index metal oxide layer is formed therebetween, or a medium refractive index layer (content of a metal oxide or a resin binder) is formed between the hard coating film and the high refractive index. And a metal oxide layer in which the refractive index is adjusted by changing the ratio and the type of the metal). It is preferable that it is 1.55-2.30, and, as for the refractive index of a high refractive index layer, it is more preferable that it is 1.57-2.20. The refractive index of the medium refractive index layer is adjusted so as to be an intermediate value between the refractive index of about 1.5 of the cellulose ester film serving as the substrate and the refractive index of the high refractive index layer. It is preferable that the refractive index of the medium refractive index layer is 1.55-1.80. It is preferable that the thickness of a metal oxide layer is 5 nm-0.5 micrometer, It is more preferable that it is 10 nm-0.3 micrometer, It is most preferable that it is 30 nm-0.2 micrometer. The haze of the metal oxide layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. It is preferable that it is 3H or more, and, as for the strength of a metal oxide layer with a pencil hardness of 1 kg load, it is most preferable that it is 4H or more. When forming a metal oxide layer by application | coating, it is preferable to contain an inorganic fine particle and a binder polymer.

The inorganic fine particles used for the metal oxide layers such as the medium refractive index layer or the high refractive index layer preferably have a refractive index of 1.80 to 2.80, more preferably 1.90 to 2.80. The weight average diameter of the primary particles of the inorganic fine particles is preferably 1 to 150 nm, more preferably 1 to 100 nm, and most preferably 1 to 80 nm. The weight average diameter of the inorganic fine particles in the layer is preferably 1 to 200 nm, more preferably 5 to 150 nm, still more preferably 10 to 100 nm, and most preferably 10 to 80 nm. The average particle diameter of an inorganic fine particle is measured by a light scattering method as it is 20-30 nm or more, and by an electron micrograph when it is 20-30 nm or less. The specific surface area of the inorganic fine particles is a value measured by the BET method, preferably 10 to 400 m 2 / g, more preferably 20 to 200 m 2 / g, and most preferably 30 to 150 m 2 / g.

Inorganic fine particles are particles formed from an oxide of a metal. As an example of the oxide or sulfide of a metal, titanium dioxide (for example, rutile, rutile / anatase mixed crystal, anatase, amorphous structure), silver oxide, indium oxide, ITO, zinc oxide, zirconium oxide, etc. are mentioned. Especially, titanium dioxide, silver oxide, and indium oxide are especially preferable. The inorganic fine particles contain oxides of these metals as main components, and may further contain other elements. A main component means the component with most content (mass%) among the components which comprise particle | grains. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S.

The inorganic fine particles may be surface treated. Surface treatment can be performed using an inorganic compound or an organic compound. Examples of the inorganic compound used for the surface treatment include alumina, silica, zirconium oxide and iron oxide. Among these, alumina and silica are preferable. As an example of the organic compound used for surface treatment, a polyol, alkanol amine, stearic acid, a silane coupling agent, and a titanate coupling agent are mentioned. Among these, a silane coupling agent is the most preferable. You may process in combination of 2 or more types of surface treatment.

The shape of the inorganic fine particles is preferably particulate, spherical, cubic, fusiform or indefinite. Two or more types of inorganic fine particles can also be used together with a metal oxide layer.

It is preferable that the ratio of the inorganic fine particle in a metal oxide layer is 5-90 volume%, More preferably, it is 10-65 volume%, More preferably, it is 20-55 volume%.

The inorganic fine particles are provided in a coating liquid for forming a metal oxide layer in a state of dispersion dispersed in a medium. As a dispersion medium of inorganic fine particles, it is preferable to use a liquid whose boiling point is 60-170 degreeC. Specific examples of the dispersion solvent include water, alcohol (for example, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester ( For example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate, aliphatic hydrocarbons (e.g. hexane, cyclohexane), aromatic hydrocarbons (e.g. benzene , Toluene, xylene), amides (e.g. dimethyl formamide, dimethyl acetamide, n-methyl pyrrolidone), ethers (e.g. diethyl ether, dioxane, tetrahydrofuran), ether alcohols (e.g. For example, 1-methoxy-2-propanol) can be mentioned. Among these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

The inorganic fine particles can be dispersed in the medium using a disperser. As an example of a disperser, a sand grinder mill (for example, a bead mill with a pin), a high speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill are mentioned. Particular preference is given to sand grinder mills and high speed impeller mills. Furthermore, preliminary dispersion processing can also be performed. Examples of the disperser used for the preliminary dispersion treatment include ball mills, triaxial roll mills, kneaders and extruders.

It is preferable that the metal oxide layer uses a polymer having a crosslinked structure (hereinafter also referred to as a "crosslinked polymer") as a binder polymer. Examples of the crosslinked polymers include crosslinked products such as polymers having a saturated hydrocarbon chain such as polyolefins (hereinafter collectively referred to as 'polyolefins'), polyethers, polyureas, polyurethanes, polyesters, polyamines, polyamides and melamine resins. Can be mentioned. Among these, the crosslinked material of polyolefin, polyether, and polyurethane is preferable, the crosslinked material of polyolefin and polyether is more preferable, and the crosslinked material of polyolefin is the most preferable. Moreover, it is more preferable that a crosslinked polymer has an anionic group. The anionic group has a function of maintaining the dispersed state of the inorganic fine particles, and the crosslinked structure has a function of imparting a film forming ability to the polymer to strengthen the film. The anionic group may be directly bonded to the polymer chain or may be bonded to the polymer chain via a linking group, but is preferably bonded to the main chain as a side chain via a linking group.

The refractive index of the low refractive index layer used for the antireflection layer of the present invention is preferably 1.46 or less, particularly preferably 1.3 to 1.45, and the low refractive index layer can be formed by the sol-gel method using silicon alkoxide as the coating composition. . Or it can be set as a low refractive index layer using a fluororesin. In particular, it is preferable that it is comprised from the hardened | cured material of the thermosetting or ionizing radiation hardening type fluorine-containing resin from the hardened | cured material and the oxide ultrafine particle of silicon.

It is preferable that the dynamic friction coefficient of the said hardened | cured material is 0.02-0.2, and it is preferable that the pure contact angle is 90-130 degrees. As said curable fluorine-containing resin, a perfluoroalkyl group containing cyan compound (for example, (heptadecafluoro-1,1,2,2- tetradecyl) triethoxy silane), and a fluorine-containing copolymer (crosslinkable group The monomer which has and the fluorine-containing monomer are used as a structural unit) is mentioned. Specific examples of the fluorine-containing monomer unit include hexafluoro ethylene, hexafluoro propylene, tetrafluoro ethylene, and fluoro olefins (for example, vinylidene fluoride perfluoro-2,2-dimethyl-1,3 Fluorinated vinyl ethers such as deoxysol, fluoroethylene and the like, fluorinated alkyl ester derivatives of (meth) acrylic acid (for example, biscot 6FM (Osaka Organic Chemicals) and M-2020 (Daikin)). As a monomer having a crosslinkable group, a (meth) acrylate monomer having a carboxyl group, an amino group, a hydroxyl group, a sulfonic acid group, etc., in addition to a (meth) acrylate monomer having a crosslinkable functional group in a molecule such as glycidyl methacrylate in advance. (For example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, etc.) are mentioned. That the same may be introduced into the cross-linked structure after the sum is described in Japanese Patent Application Publication No. 10-25388, and Japanese Patent Application Publication Hei-10-147739 call.

Moreover, not only the polymer which makes the said fluorine-containing monomer a structural unit, but the copolymer with the monomer which does not contain a fluorine atom can be used. There is no restriction | limiting in particular in the monomer unit which can be used together, For example, acrylic esters (methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate), methacrylic esters (methyl methacrylate, ethyl methacrylate, butyl methacrylate) , Ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinyl benzene, α-methyl styrene, vinyl toluene, etc.), acrylamides (N-tert butyl acrylamide, N-cyclohexyl acrylamide, etc.), meta Olefins (ethylene, propylene, isoprene, vinylidene chloride, vinyl chloride, etc.), vinyl ethers (such as methyl vinyl ether), vinyl esters (vinyl acetate, vinyl propionate, cinnamic acid) such as krill amides and acrylonitrile derivatives Vinyl).

It is preferable to add and use silicon oxide fine particles to the fluorine-containing resin used for formation of a low refractive index layer in order to improve flaw resistance. The addition amount is adjusted by the balance of refractive index and scratch resistance. As the silicon oxide fine particles, silica sol dispersed in a commercially available organic solvent can be added to the coating composition as it is, or various commercially available silica powders can be dispersed and used in the organic solvent.

It is preferable that the coating composition for low refractive index layer formation of the antireflection film of this invention contains a solvent of the low boiling point mainly. It is preferable that the solvent whose boiling point is 100 degrees C or less specifically, is 50 mass% or more of all the solvents. Thereby, even when apply | coated to the surface of a base material with an unevenness | corrugation like an anti-glare layer, it can dry quickly, the fine film thickness nonuniformity according to the flow of a coating liquid is reduced, and the increase of reflectance is suppressed. Moreover, since dry nonuniformity and white nonuniformity are suppressed when the solvent with a boiling point of 100 degreeC or more is contained, it is preferable that 0.1-50 mass% of solvents with a boiling point of 100 degreeC or more are contained.

As a low boiling point solvent used for the coating composition for low refractive index layers, ketones, such as acetone and methyl ethyl ketone, esters, such as methyl acetate and ethyl acetate, ether alcohols, such as methyl cellosolve, alcohol, such as methanol, ethanol, and isopropanol Among them, those having high solubility of solids contained in the coating composition are preferably used. As a coating solvent whose boiling point exceeds 100 degreeC, ketones, such as cyclohexane, cyclopentanone, and methyl-isobutyl ketone, ether alcohols, such as diacetone alcohol, and propylene glycol monomethyl ether, 1-butanol, 2-butanol, etc. Alcohols and the like are used.

Each layer of the antireflection film can be formed by coating by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, micro gravure coating or extrusion coating.

In the present invention, a method of forming a metal oxide layer by plasma discharge treatment is particularly preferably used.

Hereinafter, the method of forming a metal oxide layer by a plasma discharge process is demonstrated using FIG. 1, FIG.

As the method for forming the metal oxide layer on the hard coat film of the present invention, the plasma discharge treatment under atmospheric pressure or the pressure in the vicinity thereof is performed by using a plasma discharge treatment apparatus as follows.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows an example of the plasma discharge processing apparatus used for forming a metal oxide layer on the hard coat film of this invention.

In FIG. 1, this apparatus has a pair of rotating electrodes 10A and 10B, and the rotating electrodes 10A and 10B have a voltage 80 capable of pressurizing a voltage for generating plasma discharge. Although it is connected to the voltage supply means 81 and one side is connected to the earth, 82 is connected to the earth.

The rotating electrodes 10A and 10B are conveyed while winding the hard coat film, and are preferably roll electrodes or belt-shaped electrodes, and in FIG. 1, roll electrodes are shown.

The gap (electrode gap) between these rotating electrodes is a place where a discharge is made, and it is set at the space | interval which can convey the hard coat film (F). The gap between these electrodes becomes the discharge portion 50.

This electrode gap is maintained under atmospheric pressure or a pressure near the atmospheric pressure, and the reaction gas G is supplied from the reaction gas supply part 30 to the plasma coating process of the hard coat film F surface.

Here, the hard coat film F unwound from the original winding roll or the hard coat film F conveyed in the previous step is brought into contact with the rotating electrode 10A which first rotates in the conveying direction via the guide roll 20. While being transported, the thin film is formed on the surface of the hard coat film F through the discharge unit 50.

The hard coat film F which once came out of the discharge part 50 is U-turned at U turn rolls 11A-11D, and this time, the hard coat film F is rotating in the opposite direction to the rotating electrode 10A. A thin film subjected to plasma discharge treatment is formed on the surface of the hard coating film F, which is transported while contacting the rotating electrode 10B, and passes again through the discharge part 50 to form a thin film. The U-turn is usually performed for about 0.1 seconds to 1 minute.

The reaction gas G used for the process is discharged as the exhaust gas G 'after the reaction by the gas discharge port 40. The reaction gas (G) is preferably superheated to room temperature to 250 ° C, preferably 50 to 150 ° C, more preferably 80 to 120 ° C, and sent to the discharge unit 50.

Furthermore, it is preferable that the rectifying plate 51 is provided in the discharge part 50, while making the flow of reaction gas G and the exhaust gas G 'smooth, and the discharge part 50 widens, It is preferable to control so as not to generate unnecessary discharge between the electrodes 10A and 10B, and the rectifying plate 51 is preferably an insulating member.

In the drawing, the thin film formed on the hard coat film F is omitted. The hard coat film F in which the thin film was formed in the surface is conveyed to the next process or a winding roll (not shown) direction through the guide roll 21.

Therefore, the hard coat film F is subjected to plasma discharge treatment by reciprocating the discharge unit 50 in a state of being in close contact with the rotating electrodes 10A and 10B.

Although not shown, devices such as the rotary electrodes 10A and 10B, the guide rolls 20 and 21, the U-turn rolls 11A to 11D, the reactive gas supply unit 30, and the gas outlet 40 are external. It is preferable that it is enclosed and accommodated in the plasma discharge processing container which interrupts | blocks.

Although not shown, a temperature control medium for temperature control of the rotating electrodes 10A and 10B is circulated as necessary to control each electrode surface temperature to a predetermined value. The diameters of the rotating electrodes 10A and 10B are 10 to 1,000 mm, preferably 50 to 500 mm, and may be used in combination with different diameters.

2 is a view showing an example of a plasma discharge processing apparatus having a rotating electrode and a fixed electrode useful for forming a metal oxide thin film layer on the hard coat film of the present invention.

The guide roll 120, the nip roll which has the rotating electrode 110 and the some fixed electrode 111 arrange | positioned opposed to it, the original coating roll which is not shown, or the hard-coating film F conveyed in the previous process is carried out. Guided to the rotating electrode 110 via the 122, the hard coating film (F) is conveyed at the same time as the rotation of the rotating electrode 110 in contact with the rotating electrode 110, and is at atmospheric pressure or under pressure The reaction gas G manufactured by the reaction gas generator 131 is supplied to the discharge part 150 from the air supply pipe 130, and a thin film is formed on the surface of the hard coat film facing the fixed electrode 111.

To the rotary electrode 110 and the fixed electrode, a power source 180 capable of applying a voltage for generating plasma discharge is connected to the voltage supply means 181, and one side is connected to the earth, and 182 is earth. Is connected to.

In addition, the rotating electrode 110, the fixed electrode 111, and the discharge unit 150 are covered with the plasma discharge processing container 190 and are blocked from the outside world. The treated exhaust gas G 'is discharged from the gas exhaust port 140 in the lower portion of the processing chamber.

The plasma-discharge-treated hard coating film F is conveyed to the next process or the winding roll which is not shown through the nip roll 123 and the guide roll 121. As shown in FIG.

The hard coat film F is provided with partition plates 124 and 125 of the outer space at the portions of the nip rolls 122 and 123 of the outgoing portion of the plasma discharge processing container, and the nip roll 122 At the same time, the air entrained on the hard coat film F is cut off from the outside, or at the outlet, the reaction gas G or the exhaust gas G 'is prevented from leaking to the outside. In addition, although not shown, the rotation electrode 110 and the fixed electrode 111 are configured such that a temperature controlled medium for temperature control circulates as needed.

As described above, in the present invention, the hard coat film on which the thin film is formed is preferably subjected to plasma discharge treatment while being transported on the rotating electrode.

High smoothness is required for the surface where the rotating electrode is in contact with the hard coat film, and it is preferable that the maximum height (Rmax) of the surface roughness whose surface roughness of the surface of the rotating electrode is defined in JIS-B-0601 is 10 µm or less, more preferably. Preferably it is 8 micrometers or less, Especially preferably, it is 7 micrometers or less. In addition, it is necessary to prevent dust or foreign matter from adhering to the electrode for uniform film formation.

It is preferable that the surface of the electrode used for a plasma discharge process is coat | covered with a solid dielectric, and especially it is preferable to coat with a solid dielectric with respect to electroconductive base materials, such as a metal. Examples of the solid dielectric include plastics such as polytetrafluoroethylene and polyethylene terephthalate, glass, silicon dioxide, metal oxides such as aluminum oxide (Al ₂ O ₃ ), zirconium oxide (ZrO ₂ ) and titanium oxide (TiO ₂ ), and barium titanate. Double oxides; and the like.

Especially preferably, it is preferable that it is a ceramic coating process derivative which filled the hole using an inorganic material after spraying ceramics. Although inductive base materials, such as a metal, can mention silver, platinum, stainless, aluminum, metal, such as iron, etc., From a viewpoint of processing, stainless is preferable.

As the lining material, silicate-based glass, borate-based glass, phosphate-based glass, germanate-based glass, atelate glass, aluminate glass, vanadate glass, and the like are preferably used. Among these, borate-based glass is processed. Since it is easy to carry out, it is used more preferably.

The electrode used for a plasma discharge process can be heated or cooled as needed on the back surface side (inner side). When the electrode is a belt, it may be cooled with a gas on its back surface, but in a rotating electrode using a roll, it is preferable to control the temperature of the electrode surface and the temperature of the cellulose ester film by supplying a medium therein.

As a medium, insulating materials, such as distilled water and oil, especially a silicone oil, are used preferably.

Although the temperature of the hard coat film at the time of discharge treatment changes with treatment conditions, room temperature-200 degrees C or less are preferable, More preferably, it is room temperature-120 degrees C or less, More preferably, it is 50-110 degreeC.

Moreover, although remarkable curl might generate | occur | produce also by the film surface temperature rising etc. by discharge, according to this invention, generation | occurrence | production of curl was remarkable.

It is preferable that temperature nonuniformity does not generate | occur | produce especially in the width direction of a hard-coating film surface at the time of discharge treatment, It is preferable to set it as within +/- 5 degreeC, More preferably, it is within +/- 1 degreeC, Especially preferably, it is ± 0.1 degreeC Within.

In the present invention, the electrode gap is determined in consideration of the thickness of the solid dielectric, the applied voltage and frequency, the purpose of using the plasma, and the like. The distance between the solid dielectric when the solid dielectric is provided on one side of the electrode and the shortest distance between the electrodes, and the distance between the solid dielectrics when the solid dielectric is provided on both of the electrodes is the point of generating a uniform discharge plasma in any case. Is preferably from 0.5 mm to 20 mm, particularly preferably from 1 mm ± 0.5 mm.

In the present invention, the flow rate of the mixed gas generated by the gas generator is controlled in the discharge portion of the electrode gap and introduced into the plasma discharge portion from the reaction gas supply port. Although the density | concentration and flow volume of a reaction gas are adjusted suitably, it is preferable to supply a process gas to an electrode gap at a speed | rate sufficient with respect to the conveyance speed of a hard coat film. In the discharge section, it is preferable to set the flow rate and the discharge condition so that most of the supplied reaction gas reacts and is used for thin film formation.

In order to prevent air from entering into the discharge portion or leaking of the reaction gas out of the apparatus, the electrode and the hard-coating film during transportation are preferably shielded from the outside by surrounding the whole. In the present invention, the air pressure of the discharge portion is maintained at atmospheric pressure or a pressure in the vicinity thereof. Moreover, although reaction gas may decompose | disassemble in a gaseous phase and generate fine powder of metal oxide, it is preferable to set a flow volume and discharge conditions so that generation | occurrence | production is reduced.

Here, the atmospheric pressure vicinity shows the pressure of 20-200 kPa, but in order to acquire the effect as described in this invention preferably, 93-110 kPa is preferable. It is preferable that a discharge part is slightly positive pressure with respect to atmospheric pressure other than a device, and it is more preferable that atmospheric pressure + 0.1kPa-5kPa other than a plasma apparatus.

In the plasma discharge processing apparatus useful in the present invention, it is preferable to generate a stable plasma because one electrode is connected to a power supply and a voltage is applied, and the other electrode is grounded to earth to generate a discharge plasma.

In the high frequency power supply used in the present invention, the value of the voltage applied to the electrode is appropriately determined. For example, the voltage is about 0.5 to 10 kV, and the frequency to be applied is adjusted to 1 kHz to 150 MHz, and the waveform can be a pulse wave or a sine wave. have. In particular, it is preferable to apply a high frequency of 50 MHz over a frequency of 100 kHz, since a preferable discharge portion (discharge space) can be obtained. Alternatively, a method of simultaneously applying high frequency voltages of two frequencies of 1 kHz to 200 MHz and 800 kHz to 150 MHz is also preferably used.

It is preferable that it is 5-1000W * min / m <2>, and, as for the discharge density in a discharge part, it is especially preferable that it is 50-500W * min / m <2>.

It is preferable that the plasma discharge treatment unit is appropriately surrounded by a processing container made of Pyrex (R) glass or the like, and metal can be used as long as insulation with the electrode can be achieved. For example, a polyimide resin or the like may be attached to the surface of the frame of aluminum or stainless steel, or ceramics may be sprayed onto the metal frame to obtain insulation. Moreover, by surrounding the side surface of a discharge part, a side surface of a rotary electrode, a cellulose ester film conveyance part, etc., reaction gas and exhaust gas can be supplied or discharged to a discharge part suitably.

The reaction gas used for the formation method of the metal oxide thin film layer of this invention is demonstrated. The reaction gas for forming the thin film layer preferably includes nitrogen or an inert gas.

That is, the reaction gas is preferably a mixture gas of nitrogen or an inert gas and a reactive gas described later.

Here, the inert gas is a Group 18 element of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, and the like. In the present invention, helium and argon can be preferably used. These may be mixed and used, for example, they may be used in the ratio of helium 3: argon 7 grade | etc.,.

The concentration of the inert gas or the nitrogen in the reaction gas is preferably 90% or more because it generates stable plasma discharge, and preferably 90 to 99.9 volume%.

Inert gas or nitrogen is used to generate a stable plasma discharge, in which a reactive gas is ionized or radicalized to deposit or adhere to the substrate surface to form a thin film.

The reaction gas useful in the present invention can form a thin film having various functions on a hard coat film by adding a reactive gas of various materials.

For example, a low refractive index layer or an antifouling layer of an antireflection layer may be formed using a fluorine-containing organic compound or a silicon compound as the reactive gas.

Furthermore, these metal oxide layers (metal oxide nitride layers) are used, using organometallic compounds, metal hydrogen compounds, and metal halides containing Ti, Zr, In, Sn, Zn, Ge, Si or other metals. ) Or a metal nitride layer, and these layers may be a medium refractive index layer or a high refractive index layer of the antireflection layer, or may be a conductive layer or an antistatic layer.

Moreover, an antifouling layer and a low refractive index layer may be formed with a fluorine-containing organic compound, and a gas barrier layer and a low refractive index layer may be formed with a silicon compound. The present invention is particularly preferably used for the formation of an antireflection layer formed by laminating multilayers of alternating high and medium refractive index layers and low refractive index layers.

As a film thickness of the metal oxide layer formed, what is a range of 1 nm-1000 nm can be obtained preferably.

In atmospheric pressure plasma processing, a fluorine compound containing layer can also be formed by using a fluorine-containing organic compound for source gas.

As the fluorine-containing organic compound, fluorinated carbon gas, fluorinated hydrocarbon gas and the like are preferable.

Specifically, as a fluorine-containing organic compound, For example, Fluorocarbon compounds, such as carbon tetrafluorocarbon, carbon hexafluorocarbon, ethylene tetrafluoride, hexafluoro propylene, and cyclohexabutane;

Fluorinated hydrocarbon compounds such as difluoromethane, tetrafluoroethane, propylene tetrafluoride, propylene trifluoride, and cyclobutane octafluoride;

Moreover, the fluorine substituent of organic compounds, such as halides of fluorinated hydrocarbon compounds, such as trichloromethane monochloride, dichloromethane monochloride, tetrafluoro tetrabutane, and tetrafluoro tetrabutane, alcohol, an acid, a ketone, etc. are mentioned.

These can be used individually or in mixture. As said fluorinated hydrocarbon gas, each gas, such as difluoromethane, tetrafluoroethane, tetrafluoropropylene, and propylene trifluoride, is mentioned.

In addition, halides of fluorinated hydrocarbon compounds such as trichloromethane monochloride, dichloromethane monochloride, and tetrafluorocyclobutane, and fluorine substituents of organic compounds such as alcohols, acids, ketones can be used. It is not limited to.

In addition, these compounds may have an ethylenically unsaturated group in a molecule | numerator. In addition, the said compound can also be mixed and used.

When using a fluorine-containing organic compound as the reactive gas, from the viewpoint of forming a uniform thin film on the cellulose ester film by plasma discharge treatment, the content of the fluorine-containing organic compound as the reactive gas in the reaction gas is 0.01 to 10% by volume. Preferably, it is 0.1-5 volume% more preferably.

In addition, when the fluorine-containing organic compound used preferably is a gas at normal temperature and normal pressure, it can be used as it is as a component of a reactive gas.

In the case where the fluorine-containing organic compound is a liquid or a solid at room temperature and normal pressure, the fluorine-containing organic compound may be used by evaporating by evaporation means, for example, by heating or reduced pressure, or may be dissolved in an appropriate organic solvent.

As a silicon compound useful as a reactive gas, For example, organometallic compounds, such as dimethyl silane and tetramethyl silane, metal hydrogen compounds, such as monosilane and a disilane, metal halide compounds, such as a dichlorosilane, a trichlorosilane, and silicon tetrafluoride, for example. Alkoxy silanes, such as tetramethoxy silane, tetraethoxy silane, tetraisopropoxy silane, dimethyl diethoxy silane, methyl triethoxy silane, and ethyl triethoxy silane, organosilane, etc. are preferable, but are limited to these It doesn't work.

In addition, these can be used in combination suitably. Alternatively, other organic compounds may be added to change or control the physical properties of the film.

In the case of using a silicon compound as the reactive gas, from the viewpoint of forming a uniform thin film on the cellulose ester film by plasma discharge treatment, the content of the silicon compound as the reactive gas in the reaction gas is preferably 0.01 to 10% by volume. Preferably it is 0.1-5 volume%.

The organometallic compound useful as the reactive gas is not particularly limited, but Al, As, Au, B, Bi, Sb, Ca, Cd, Cr, Co, Cu, Fe, Ga, Ge, Hg, In, Li, Mg, Mn Organometallic compounds for forming metal compounds, such as Mo, Na, Ni, Pb, Pt, Rh, Se, Si, Sn, Ti, Zr, Y, V, W, Zn, are mentioned preferably.

For example, a titanium compound is preferable for forming a high refractive index layer of the antireflection layer, and specifically, an organic amino metal compound such as tetradimethylamino titanium, metal hydrogen compound such as monotitanium, dititanium, or dichloride. Metal alkoxides such as metal halogen compounds such as titanium, titanium trichloride and titanium tetrachloride, tetraethoxy titanium, tetraisopropoxy titanium and tetrabutoxy titanium.

The above-mentioned silicon compound and organometallic compound are preferably metal hydrogen compounds and metal alkoxides from the viewpoint of handling, and metal alkoxides are preferably used among them in that they are free of corrosiveness and noxious gas and have less process contamination. .

In the case of using an organometallic compound as the reactive gas, from the viewpoint of forming a uniform thin film on the cellulose ester film by plasma discharge treatment, the content rate of the organometallic compound as the reactive gas in the reaction gas is preferably 0.01 to 10% by volume. More preferably, it is 0.1-5 volume%.

In addition, in order to introduce metal compounds, such as a silicon compound and a titanium compound, into a discharge part, they can be used in any state of a gas, a liquid, or a solid at normal temperature and pressure.

In the case of a gas, it can introduce into a discharge part as it is, but in the case of a liquid or a solid, it can vaporize and use by vaporization means, such as heating, pressure_reduction | reduced_pressure, and ultrasonic irradiation.

When using a metal compound such as a silicon compound or a titanium compound by evaporation by heating, a metal alkoxide having a liquid and a boiling point of 200 ° C. or lower, such as tetraethoxy silane and tetraisopropoxy titanium, is a metal oxide thin film layer of the present invention. Suitable for forming method. The said metal alkoxide can also be diluted with an organic solvent, and can be used organic solvents, such as methanol, ethanol, n-hexane, or these mixed organic solvent can be used.

In addition, by containing 0.1 to 10% by volume of oxygen, hydrogen, carbon dioxide, carbon monoxide, nitrogen, nitrogen dioxide, nitrogen monoxide, water, and the like in the reaction gas, physical properties such as hardness and density of the thin film layer can be controlled.

According to the above method, amorphous metal oxide layers, such as silicon oxide and titanium oxide, can be manufactured preferably.

The hard coat film of this invention can be used suitably for the optical film which has an antireflection layer which laminated | stacked the low refractive index layer and the high refractive index layer, an electrically conductive layer, the optical film which has an antistatic layer, etc., for example.

In the present invention, by providing a plurality of plasma discharge devices, a multilayer thin film can be provided continuously, and a multilayer laminate can be formed without nonuniformity of the thin film.

For example, when producing an antireflection film having an antireflection layer on a hard coat film, a high refractive index layer having a refractive index of 1.6 to 2.3 and a low refractive index layer having a refractive index of 1.3 to 1.5 are successively laminated on the surface of the cellulose ester film to efficiently It can manufacture.

As the low refractive index layer, a layer containing mainly silicon oxide formed by plasma discharge treatment using an organic silicon compound such as a fluorine-containing compound layer formed by plasma discharge treatment or a gas containing a fluorine-containing organic compound is preferable. As the high refractive index layer, a layer having a metal oxide layer formed by plasma discharge treatment of a gas containing an organometallic compound, for example, a layer having titanium oxide and zirconium oxide is preferable.

Although there exists a method of thinning mentioned above, this invention is not limited to these, A laminated constitution is not limited to these, either. For example, an antifouling layer may be formed by performing a plasma discharge treatment under atmospheric pressure at or near the atmosphere in the presence of a fluorine-containing organic compound gas on the outermost surface.

According to the above method, in the present invention, multilayer thin films can be laminated, and there is no film thickness unevenness of each layer, and a uniform antireflection film can be obtained.

<Polarizing plate>

The polarizing plate of this invention is demonstrated.

A polarizing plate can be manufactured by a general method. Alkali saponification treatment of the back surface side of the hard coat film of the present invention, and it is preferable to glue the treated hard coat film to at least one side of the polarizing film produced by dipping and stretching in an oxo solution using a fully saponified polyvinyl alcohol aqueous solution. . The hard coat film may also be used on the other side, or another polarizer protective film may be used. About the hard coat film of this invention, it is preferable that the polarizing plate protective film used for the other surface has a phase difference whose in-plane retardation Ro is 590 nm, 20-70 nm, and Rt are 100-400 nm. These can be produced, for example, by the methods described in Japanese Patent Application Laid-Open No. 2002-71957 and Japanese Patent Application No. 2002-155395. Or it is preferable to use the polarizing plate protective film which also serves as the optical compensation film which has the optically anisotropic layer formed by orienting liquid crystal compounds, such as a discotic liquid crystal. For example, an optically anisotropic layer can be formed by the method of Unexamined-Japanese-Patent No. 2003-98348. By using it in combination with the hard coat film of this invention, the polarizing plate which is excellent in planarity and has a stable viewing angle enlargement effect can be obtained.

The polarizing film, which is a main component of the polarizing plate, is an element that allows only light of a polarization plane in a predetermined direction to pass, and a representative polarizing film known at present is a polyvinyl alcohol polarizing film, which is obtained by dyeing urea on a polyvinyl alcohol film. Some dyes are colored. As the polarizing film, a polyvinyl alcohol-based aqueous solution is formed into a film, uniaxially stretched and dyed, or after uniaxially stretched after dyeing, preferably, a durable treatment with a boron compound is used. On the surface of this polarizing film, one side of the hard coat film of this invention is bonded together, and a polarizing plate is formed. Preferably, it sticks together by the water-based adhesive whose main component is a fully saponified polyvinyl alcohol etc.

The polarizing plate using the conventional hard coating film is inferior to planarity, and when a reflection image is seen, a fine wavy pattern is confirmed, and pencil hardness can only be obtained about 2H, and it is tested by the durability test on 60 degreeC and 90% RH conditions. Although the wavy pattern also increased, the polarizing plate using the hard coat film of this invention was excellent in planarity, and also excellent in pencil hardness. Moreover, the wavy pattern did not increase even by the durability test on 60 degreeC and 90% RH conditions.

<Display device>

By incorporating the polarizing plate of the present invention into a display device, various display devices of the present invention excellent in visibility can be manufactured. The hard coat film of the present invention is preferably used as a reflective, transmissive, semi-transmissive LCD or LCD of various driving methods such as TN type, STN type, OCB type, HAN type, VA type, and IPS type. In addition, the antireflection film in which the antireflection layer is formed on the hard coat film of the present invention is markedly small in color unevenness of the reflected light of the antireflection layer, and has excellent flatness, and is suitable for plasma displays, field emission displays, organic EL displays, and inorganic ELs. It is also preferably used for various display devices such as a display and an electronic paper. Particularly, in the display device of the large screen having the screen of 30 type or more, the reflection image of the fluorescent lamp was distorted by the color unevenness or the wavy pattern, and there is no distortion like the reflection of the mirror, so that eyes are not tired even by long-term viewing Worked.

<Example>

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

[Production of Cellulose Ester Film]

The cellulose ester solution was manufactured so that it could become a dope composition as shown in Table 2 using the cellulose ester, the plasticizer, the ultraviolet absorber, the microparticles | fine-particles, and the solvent of Table 1.

That is, the solvent was put into a sealed container, the remaining materials were added in order while stirring, and completely dissolved and mixed while heating and stirring. The fine particles were dispersed and added as part of the solvent. The solution was cooled to a temperature at which it was cast, and allowed to stand overnight, and after performing a defoaming operation, the solution was filtered using Azumi filter paper No. 244 of Azumi Rossi Co., Ltd. to obtain a cellulose ester solution, respectively.

Next, the cellulose ester solution temperature-controlled at 33 degreeC was transferred to the die | dye, and it was cast uniformly on the stainless belt by the die slit. The flexible part of the stainless steel belt was heated with warm water at 37 ° C. from the back side. After casting, a warm air at 44 ° C. was blown into a dope film (hereinafter referred to as a web after casting on a stainless steel belt) on a metal support, and the residual solvent amount of the peeling was peeled to 120% by mass, giving a tension at the time of peeling. It extended | stretched so that it might become the longitudinal stretch ratio of, Then, the web edge part was hold | gripped with a tenter, and it extended | stretched so that it might become the draw ratio shown to the table in the width direction. After stretching, after preserving for several seconds while maintaining the width thereof, the tension in the width direction was relaxed, then the width preservation was released, and the drying was carried out by conveying for 20 minutes in a third drying zone set at 125 ° C. Cellulose ester films Nos. 1 to 27 having a predetermined film thickness of 1.4 to 2 m and having knurling having a width of 1.5 cm and a height of 8 µm at the ends were prepared.

About each produced cellulose ester film, the cellulose ester, plasticizer, ultraviolet absorber, etc. which were used were also summarized in Table 2 about the draw ratio of a web, the film thickness of the produced film, and film forming width.

[Production of Hard Coating Film]

<< application of hard coating layer >>

On each surface of the cellulose ester films No. 1 to 27, the coating liquid for the following hard coating layer (ultraviolet curing resin layer) was filtered with a polypropylene filter having a pore diameter of 0.4 mu m to prepare a hard coating layer coating liquid, The coating layer was coated using a gravure coater, dried at 90 ° C., and then irradiated with 100 mW / cm 2 and irradiated with 50 mJ / cm 2 with an ultraviolet lamp to form a hard coating layer having a thickness of 6 μm. However, 100 mJ / cm <2> about cellulose ester films 11 and 26, 120mJ / cm <2> about 22-24, and 150mJ / cm <2> about 25 and 27 were hardened | cured. Thus, hard-coat films No. 1-27 shown in Table 3 were manufactured.

<Coating liquid for hard coating layer>

100 parts by mass of dipentaerythritol hexaacrylate

4 parts by mass of photoreaction initiator

(Irgacure 184 (product of Ciba specialty chemicals)

75 parts by mass of ethyl acetate

Propylene Glycol Monomethyl Ether 75 parts by mass

0.5 parts by mass of a silicone compound

(BYK-30 7 (product of Big Chemie Japan))

Furthermore, in the above-mentioned cellulose ester film Nos. 1 and 8 to 11, the film thickness (H) of the hard coating layer was set in the range of 2 to 10 μm as shown in Table 4 using the coating liquid for hard coating layer. By varying (the ratio (d / H) of the film thickness (H) of the hard coat layer and the film thickness (d) of the cellulose ester film) was changed, the hard coat films No. 28-44 were similarly produced. In addition, the hard coat layer was hardened by the ultraviolet irradiation amount 50mJ / cm <2>.

In addition, using the cellulose ester films No. 1 and 8, after applying the coating liquid for the hard coating layer so that the dry film thickness is 7㎛, and also the roughness from the ultraviolet lamp at the time of curing as shown in Table 5 As mentioned above, by changing in the range of 20-200 mW / cm <2> and short time, the ultraviolet-ray irradiation amount was 50 mJ / cm <2> similarly to the above, and hard coat films No. 45-52 were manufactured.

〔evaluation〕

The following evaluation was performed about the obtained optical film.

Flatness index; Microscopic unevenness evaluation >>

Laser displacement meter: Scanning with the laser displacement meter in the width direction using Keyence Co., Ltd., model: LT-8100, resolution: 0.2 micrometer, the fine relief of the surface was measured, and the planarity of the hard coat film was evaluated.

In the measuring method, the distance between the camera lens and the sample film is placed on a moving rail of a sigma photonic product in which the film is placed on a flat and horizontal die, the both ends of the width are fixed to the die with a tape, and the measuring camera is set in parallel with the die. It set so that it might be set to 25 mm, and it measured by scanning at a movement speed of 5 cm / min. The value obtained by the measurement is a state and magnitude | size of the minute unevenness | corrugation of a film surface.

◎: Unevenness due to deformation of the film is less than 0.5 μm

(Circle): Unevenness by deformation of a film is less than 0.5-1.0 micrometer

△: unevenness due to deformation of the film is less than 1.0 ~ 3.0㎛

X: Unevenness due to deformation of the film is 3.0 μm or more

Planarity; Visual observation evaluation >>

Each sample was cut to a size of 90 cm in width and 100 cm in length, and five 50 W fluorescent lamps were arranged and fixed at a height of 1.5 m so as to shine at a 45 ° angle on the sample table, and each film sample was placed on the sample table. The unevenness | corrugation reflected by the film surface was visually observed, and it determined as follows. According to this method, it is possible to determine the bend and the wrinkle.

◎: all five fluorescent lamps were straight

(Circle): There are some places where a fluorescent lamp is bent slightly.

(Triangle | delta): Fluorescent lamp looks a little bent overall.

×: Fluorescent lamp looks large

<< nonuniformity of pencil hardness and width >>

Using a pencil of different hardness, the hardness test was performed based on the test method presented in JIS K5400 under 1 kg load. It divided into 10 width directions of each hard coat film, and measured the pencil hardness in each position.

In addition, the following reference | standard evaluated about the dispersion day of width | variety.

○ No change in width

X tends to decrease at the width end

`` Injury resistance ''

The steel wool of # 0000 reciprocates the surface of the hard coating layer 10 times while applying a load of 1000 g, and closes the black tape to the inside, and visually observes the occurrence of a flaw with a green lamp. The number of defects in the party was determined.

The evaluation results of the hard coat films 1 to 27 are shown in Table 3 below. From the results, it was confirmed that the hard coat film of the present invention was excellent in planarity and hardness and scratch resistance.

The evaluation results of the hard coat films 28 to 44 produced by changing the film thickness of the hard coating and the film thickness of the cellulose ester film are shown in Table 4 below. From the results, the hard coat film having a film thickness of 10 to 70 µm and a ratio d / H of the film thickness H of the active-ray cured resin layer to the film thickness d of the cellulose ester film of 4 to 10 was particularly planar. At the same time, it was confirmed that the hardness and the scratch resistance were also excellent.

In addition, the evaluation results for the hard coat films 45 to 52 produced by changing the illuminance of the ultraviolet lamp and the film thickness of the cellulose ester film are shown in Table 5 below. In particular, it was confirmed that the hard coat film cured at roughness of 50 to 150 mW / cm 2 of the active line irradiation part was particularly excellent in flatness and hardness and scratch resistance. In addition, despite the small dose, the hardness was excellent, and thus the productivity of the production line was remarkably excellent.

[Production of antireflection film]

An antireflection layer was formed on the hard coat film prepared above.

On the hard coat films Nos. 1 to 52, the following coating solution for the medium refractive index layer was applied using a bar coater, dried at 70 ° C, and then irradiated with ultraviolet rays to cure the coating layer, and the medium refractive index layer (refractive index 1.72, film) Thickness of 80 nm). The following coating liquid for high refractive index layers was apply | coated using a bar coater, and it dried at 70 degreeC, irradiated with ultraviolet-ray, hardened the coating layer, and formed the high refractive index layer (refractive index 1.9, film thickness 70nm). Further, the coating solution for the low refractive index layer described below was applied using a bar coater, dried at 70 ° C., and then irradiated with ultraviolet rays to cure the coating layer to form a low refractive index layer (refractive index 1.45, film thickness of 95 nm). The antireflection films Nos. 1 to 52 having a reflectance of 0.5% or less were produced.

<Production of Medium Refractive Index Layer / High Refractive Index Layer / Low Refractive Index Layer>

(Production of Titanium Dioxide Dispersion)

30 parts by mass of titanium dioxide (primary particle mass average particle diameter: 50 nm, refractive index: 2.70), 4.5 parts by mass of anionic diacrylate monomer (PM21, Nippon Kayaku Co., Ltd.), cationic methacrylate monomer (DMAEA, 0.3 parts by mass of Kyojin Co., Ltd. and 65.2 parts by mass of methyl ethyl ketone were dispersed with a sand grinder to prepare a titanium dioxide dispersion.

(Production of Coating Liquid for Medium Refractive Index Layer)

Into 151.9 g of cyclohexanone and 37.0 g of methyl ethyl ketone, 0.14 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Kaigi Co., Ltd.) and 0.04 g of a photosensitizer (Kayacure DETX, Nippon Kayaku Co., Ltd.) were dissolved. Further, 6.1 g of the above titanium dioxide dispersion and 2.4 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.) were added thereto, stirred at room temperature for 30 minutes, and then the pore size was adjusted. It filtered with the 0.4 micrometer polypropylene filter, and produced the coating liquid for medium refractive index layers. When this coating liquid was applied to a cellulose ester film and dried, the refractive index after ultraviolet curing was measured, and a medium refractive index layer having a refractive index of 1.72 was obtained.

(Production of Coating Liquid for High Refractive Index Layer)

0.06g of a photoinitiator (Irgacure 907, the product of Ciba Gaiji) and 0.02g of the photosensitizer (Kayacure DETX, Nippon Kayaku Co., Ltd.) were dissolved in 1152.8g of cyclohexanone and 37.2g of methyl ethyl ketone. In addition, by increasing the ratio of the titanium dioxide dispersion of the above-described titanium dioxide dispersion and the mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.), the refractive index of the high refractive index layer The amount was adjusted so that it was stirred at room temperature for 30 minutes, and it filtered with the polypropylene filter of 0.4 micrometer of pore diameters, and prepared the coating liquid for high refractive index layers. This coating solution was applied to a cellulose ester film, dried, and the refractive index after UV curing was measured, whereby a high refractive index layer having a refractive index of 1.9 was obtained.

(Production of Coating Liquid for Low Refractive Index Layer)

To 200 g of a methanol dispersion (methanol silica sol, manufactured by Nissan Chemical Co., Ltd.) of silica fine particles having an average particle diameter of 15 nm, 3 g of a silane coupling agent (KBM-503, manufactured by Shin-Etsu Silicone Co., Ltd.) and 2 g of 0.1 M / L hydrochloric acid were added. After stirring at room temperature for 5 hours, the mixture was left at room temperature for 3 days to prepare a dispersion of silica fine particles treated with silane coupling. To 35.04 g of the dispersion, 58.35 g of isopropyl alcohol and 39.34 g of diacetone alcohol were added. In addition, a solution obtained by dissolving 1.02 g of a photopolymerization initiator (Irga Cure 907, manufactured by Shiba Kaigi Co., Ltd.) and 0.51 g of a photosensitizer (Kayacure DETX, Nippon Kayaku Co., Ltd.) in 772.85 g of isopropyl alcohol was added. 25.6 g of a mixture of pentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.) was added and dissolved. 67.23 g of the obtained solution was added to the mixture of the above dispersion, isopropyl alcohol and diacetone alcohol. The mixture was stirred at room temperature for 20 minutes, and filtered with a polypropylene filter having a pore diameter of 0.4 µm to prepare a coating liquid for low refractive index layer. This coating liquid was applied to a cellulose ester film and dried to measure the refractive index after ultraviolet curing, and the refractive index was 1.45.

The polarizing plate was produced using each antireflection film.

[Production of Polarizing Plate]

The polyvinyl alcohol film of thickness 120micrometer was uniaxially stretched (temperature 110 degreeC, draw ratio 5 times). It was immersed for 60 seconds in the aqueous solution which consists of 0.075g of urea, 5g of potassium iodide, and 100g of water, and then it was immersed in the 68 degreeC aqueous solution which consists of 6g of potassium iodide, 7.5g of boric acid, and 100g of water. This was washed with water and dried to obtain a polarizing film.

Next, the polarizing film was bonded together with the said antireflection film and the cellulose-ester film of the back surface side according to the following 1-5 processes. The polarizing plate protective film on the back side was used as a polarizing plate using the cellulose ester film which measured retardation (590 nm, and had in-plane retardation Ro = 43 nm and retardation Rt = 135 nm of thickness direction), respectively.

1st process: It immersed in 60 degreeC 2 mol / L sodium hydroxide solution for 90 second, and then washed with water and dried, and obtained the cellulose-ester film which saponified the side which sticks with a polarizer.

On the other hand, the surface of the hard coat film in which the antireflection layer was formed was subjected to the saponification treatment while attaching a peelable polyethylene film and protecting it from alkali.

2nd process: The said polarizing film was immersed for 1-2 second in polyvinyl alcohol adhesion manufacture of 2 mass% of solid content.

3rd process: The excess adhesive adhered to the polarizing film in the 2nd process was lightly wiped off, it was raised on the cellulose-ester film processed in the 1st process, and it laminated | stacked and arrange | positioned so that the anti-reflective layer of a hard coat film might become the outer side. .

Fourth process: Excess adhesive agent and air bubbles were removed and pasted together at the stage of the laminate of the antireflection film, the polarizing film, and the cellulose ester film sample laminated in the third step with a hand roller. The pressure of the hand roller was 20-30 N / cm <2>, and the roller speed was about 2 m / min.

5th process: The sample which stuck the polarizing film, the cellulose-ester film, and the antireflection film which were manufactured by the 4th process in 80 degreeC dryer was dried for 2 minutes, and the polarizing plate was produced. Polarizing plates No. 1-52 were manufactured using antireflection films No. 1-52, respectively.

[Manufacture of Liquid Crystal Display Device]

The liquid crystal panel which performs a viewing angle measurement was manufactured as follows, and the characteristic as a liquid crystal display device was evaluated.

The previously bonded double-sided polarizing plates of the Fujitsu 15 type display VL-150SD were peeled off, and the polarizing plates 1 to 52 produced above were pasted onto the glass surface of the liquid crystal cell, respectively.

At that time, the bonding direction of the polarizing plate is performed such that the surface of the optical compensation film (retardation film) is on the liquid crystal cell side, and the absorption axis is directed in the same direction as the polarizing plate that has been pasted, so that the liquid crystal display devices Nos. Each was prepared.

〔evaluation〕

Evaluation of Visibility

The liquid crystal display devices thus obtained were returned to 23 ° C. and 55% RH after being left to stand at 60 ° C. and 90% RH for 10 hours. As a result, when the surface of the display device was observed, the use of the antireflection film laminated on the hard coat film of the present invention was excellent in flatness, whereas the comparative polarizing plate was found to have fine wavy patterns, and the eyes were easily tired. .

◎: wavy pattern on the surface is not visible at all

○: slightly wavy pattern on the surface

△: slight wavy pattern is seen on the surface

×: Fine wavy pattern is seen on the surface

<< Evaluation of Reflective Color Unevenness >>

About each liquid crystal display device, the screen was made into black display, and the reflection nonuniformity of the surface was visually evaluated.

(Double-circle): The color nonuniformity of a reflected light is not recognized, and black is seen in place.

(Circle): The color nonuniformity of reflected light is recognized slightly.

(Triangle | delta): The level which the color nonuniformity of reflected light is recognized but there is no problem practically

X: The color nonuniformity of the reflected light is quite annoying.

Tables 3, 4 and 5 show the evaluation results for the above hard coat films No. 1 to 52 and liquid crystal display devices 1 to 52. FIG.

In addition, the viewing angle was measured in each liquid crystal display device by EZ-contrast by ELDIM. The viewing angle was shown in the range of the inclination angle from the normal direction with respect to the panel surface where the contrast ratio in the white display and the black display of a liquid crystal cell shows 10 or more. As a result, in the liquid crystal display devices 1-18, 28-52 of this invention using the polarizing plate of this invention, when it measured in the inclination 45 degree direction, it was confirmed that it is a viewing angle of 160 degree or more. Moreover, even if there was a halation of the fluorescent lamp in the oblique direction, black was seen in place, there was no color unevenness of the reflected light, and the eyes were not tired. On the other hand, in the comparative liquid crystal display devices 19-27, black from an inclination direction was not seen in place by a fine wavy pattern, visibility was inferior, and the visibility improvement effect by the viewing angle enlargement was reduced.

[Evaluation of Plasma Display Indication Device]

The produced antireflection films Nos. 1 to 27 were pasted with an adhesive to the foremost surface of a commercial panel (PDP-503HD, manufactured by Pioneer Co., Ltd.) to manufacture the display devices 1 to 27. The display device thus obtained is placed on a table 75 cm high from the floor, and two sets of fluorescent fluorescent lamps (FL40SS, ELW / 37 type, 37W, manufactured by Matsushita Electric Industries, Ltd.) are set in a ceiling of 3 m from the floor. 8 sets were arrange | positioned at the interval of 1.5m. At this time, when the evaluator was in front of the display device, the fluorescent lamp was placed in the ceiling from the head of the evaluator toward the rear, and the halo of the fluorescent lamp was evaluated as follows. As a result, in the antireflection film using the hard coat layer of this invention, it turned out that there is no distortion until the halation of a near fluorescent lamp, and that eye does not become tired even by prolonged viewing.

(result)

The hard coating film of the present invention has excellent hardness, and can be cured with a low irradiation light amount, because of its excellent flatness and hardness. Thus, even if the hard coating film is manufactured using a thin film or a wide cellulose ester film base material, the hardness is excellent. Not only was it excellent, there was no hardness nonuniformity in the width direction, and the hard coat film which was excellent also in planarity was obtained. Further, by forming the antireflection layer on the hard coat film, there is no color unevenness of the reflected light, and the use of the polarizing plate allows the viewing angle enlargement effect to be utilized, thereby obtaining a liquid crystal display device having excellent visibility from an inclination, and furthermore, 30 type. Even when applied to a display device such as a plasma display, the reflection image does not appear to be distorted in a wave shape, and it was confirmed that the eyes were not tired.

It is possible to provide a hard coating film having excellent hardness, and having a uniform flaw resistance and excellent planarity even if it is a thin film or a wide width, and a method for producing the same with good productivity. With this hard coating film, color unevenness is significantly reduced. The antireflection film, the polarizing plate excellent in the flatness using them, and the display apparatus excellent in the flatness of the surface can be provided.

Claims (13)

(i) one kind of plasticizer is a polyhydric alcohol ester plasticizer, and the other is a plasticizer other than the phosphate ester plasticizer; (ii) the total acyl group substitution degree of the cellulose ester is 2.6 to 2.9; (iii) the number average molecular weight (Mn) of the cellulose ester is 80,000 to 200,000; (iv) the value of the weight average molecular weight (Mw) / number average molecular weight (Mn) of the cellulose ester is 1.4 to 3.0; (v) the cellulose ester film is a biaxially stretched cellulose ester film; (vi) the actinic ray cured resin layer is produced by curing the actinic ray cured resin by irradiation after applying the actinic ray cured resin onto the cellulose ester film, The hard coat film which formed the active-line hardening resin layer on the cellulose-ester film containing a ultraviolet absorber and 2 or more types of plasticizers. The hard coat film according to claim 1, wherein the dose of active radiation is 5 to 100 mJ / cm 2. The hard coat film of claim 1, wherein the active line irradiation part has a roughness of 50 to 150 mW / cm 2. The hard coating film according to claim 1, wherein the plasticizer other than the phosphate ester plasticizer is selected from the group consisting of citric acid ester plasticizers, glycolate plasticizers, phthalic acid ester plasticizers and fatty acid ester plasticizers. The film thickness of a cellulose ester film is 10-70 micrometers, The ratio (d / H) of the film thickness (H) of an active-line hardening resin layer and the film thickness (d) of a cellulose ester film is 4-4. 10 hard coating film. The hard coat film of claim 1, wherein the cellulose ester film has a width of 1.4 to 4 m. (i) forming an antireflection layer on one surface of the hard coat film having the active line cured resin layer; (ii) The polarizing plate containing the hard coat film of Claim 1 which provided the polarizing film and the cellulose ester retardation film in order on the back surface of a hard coat film. The liquid crystal display device which provided the hard coat film of Claim 1 on the surface. The liquid crystal display device which has a polarizing plate of Claim 7. (i) casting a solution containing a cellulose ester, an ultraviolet absorber, two or more plasticizers and a solvent on a support to form a cellulose ester film; (ii) drying the cellulose ester film to a peelable state from the support; (iii) peeling off the cellulose ester film from the support; (iv) biaxially stretching the cellulose ester film with a solvent; (v) drying the cellulose ester film; (vi) applying the actinic curable resin on the cellulose ester film; (vii) irradiating the active line at an amount of light of the active line at 5 to 100 mJ / cm 2 to cure the active line curing resin, (a) one of the plasticizers is a polyhydric alcohol ester plasticizer, and the other is a plasticizer other than the phosphate ester plasticizer; (b) the cellulose esters have a total acyl substitution degree of 2.6 to 2.9; (c) the cellulose ester has a number average molecular weight (Mn) of 80,000 to 200,000; (d) The cellulose ester has a weight average molecular weight (Mw) / number average molecular weight (Mn) of 1.4 to 3.0 method of producing a hard coat film. The method according to claim 10, wherein the cellulose ester film is stretched in the longitudinal direction while containing a solvent, and then stretched in the transverse direction using a tenter. The method of claim 10, wherein the actinic radiation curable resin is cured while applying tension. The method of claim 11, wherein the actinic radiation curable resin is cured while applying tension.